Cosmetic makeup and/or care process using a siloxane resin and a film-forming polymer

ABSTRACT

The present invention relates to a process for making up and/or caring for keratin materials, in which a composition is applied to the keratin materials, and especially to the lips, this composition containing, in a physiologically acceptable medium:
         a) a siloxane resin comprising the following units:   (i) (R 1   3 SiO 1/2 ) a      (ii) (R 2   2 SiO 2/2 ) b      (iii) (R 3 SiO 3/2 ) c  and   (iv) (SiO 4/2 ) d  
 
with
   R 1 , R 2  and R 3  independently representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,   a being between 0.05 and 0.5,   b being between 0 and 0.3,   c being greater than 0,   d being between 0.05 and 0.6,   a+b+c+d=1,   on condition that more than 40 mol % of the groups R 3  of the siloxane resin are propyl groups, and   b) at least one liquid fatty phase, and   c) at least one film-forming polymer chosen from the group comprising:
           a film-forming block ethylenic polymer, comprising at least a first block and at least a second block, is characterized in that the first block is obtained from at least one acrylate monomer of formula CH 2 ═CH—COOR 2  in which R 2  represents a C 4  to C 12  cycloalkyl group and at least one methacrylate monomer of formula CH 2 ═C(CH 3 )—COOR 2  in which R′ 2  represents a C 4  to C 12  cycloalkyl group, and characterized in that the second block is obtained from an acrylic acid monomer and from at least one monomer with a glass transition temperature of less than or equal to 20° C.,   a vinyl polymer comprising at least one carbosiloxane dendrimer-based unit,   a dispersion of acrylic or vinyl radical homopolymer or copolymer particles dispersed in the said liquid fatty phase.

The invention relates to a cosmetic composition for keratin materials,especially the skin, the hair and the nails. The invention relates inparticular to makeup compositions for keratin materials.

One of the objects of the patent application is to produce makeupcompositions for keratin materials (skin, mucous membranes, fibre,eyelashes and integuments) that allow the application of a totaltransfer-resistant film with good staying power.

In the field of lipsticks and makeup in general, formulators are insearch of compositions that have good staying-power properties, tosatisfy consumers' expectations. These compositions should also betransfer-resistant, while at the same time offering good comfortproperties.

Formulators are thus in search of starting materials and/or systems forobtaining compositions whose application is characterized by improvedstaying power and a good level of comfort. The term “comfort” means thecomfort on application, i.e. a composition that is easy to apply interms of glidance and of amount applied, without, however, the appliedfilm being too thick and/or tacky. The term “comfort” also means thecomfort after application, so that the user does not experience anytautness or drying out, in particular.

It is known to those skilled in the art to use polymers to obtain thesestaying-power properties in the course of the day.

These polymers are of very diverse chemical nature and are conveyedeither in a fatty phase or in an aqueous phase.

Examples that may be mentioned include silicone resins, especially of MQtype, polyacrylates, latices, etc.

Although these polymers do indeed afford staying-power properties, inparticular transfer resistance, they are usually accompanied bydiscomfort either during the application of the product (difficultspreading, tackiness, etc.) or during the day (tautness, mask effect,etc.).

It is thus necessary to search for a technical solution for obtainingthese staying-power properties while at the same time maintainingcomfortable use.

These objects, and others, are achieved by means of a compositioncontaining, in a physiologically acceptable medium, a) a siloxane resincomprising the following units:

(i) (R¹ ₃SiO_(1/2))_(a)

(ii) (R² ₂SiO_(2/2))_(b)

(iii)(R³SiO_(3/2))_(c) and

(iv) (SiO_(4/2))_(d)

with

R¹, R² and R³ independently representing an alkyl group containing from1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,

a being between 0.05 and 0.5,

b being between 0 and 0.3,

c being greater than 0,

d being between 0.05 and 0.6,

a+b+c+d=1,

on condition that more than 40 mol % of the groups R² of the siloxaneresin are propyl groups, b) at least one liquid fatty phase and c) atleast one film-forming polymer chosen from the group comprising:

-   -   a film-forming block ethylenic polymer, which preferably        comprises at least a first block and at least a second block        with different glass transition temperatures (Tg), the said        first and second blocks being linked together via an        intermediate block comprising at least one constituent monomer        of the first block and at least one constituent monomer of the        second block,    -   a vinyl polymer comprising at least one carbosiloxane        dendrimer-based unit,    -   a dispersion of acrylic or vinyl radical homopolymer or        copolymer particles dispersed in the said liquid fatty phase.

Preferably, the block ethylenic film-forming polymer, comprising atleast a first block and at least a second block, is characterized inthat the first block is obtained from at least one acrylate monomer offormula CH₂═CH—COOR₂ in which R₂ represents a C₄ to C₁₂ cycloalkyl groupand at least one methacrylate monomer of formula CH₂═C(CH₃)—COOR₂ inwhich R′₂ represents a C₄ to C₁₂ cycloalkyl group, and characterized inthat the second block is obtained from an acrylic acid monomer and fromat least one monomer with a glass transition temperature of less than orequal to 20° C. Such polymers and the process for preparing them aredescribed, for example, in document EP 1 882 709.

Preferably, the siloxane resin comprises the following units:

(i) (R¹ ₃SiO_(1/2))_(a)

(iii) (R³SiO_(3/2))_(c) and

(iv) (SiO_(4/2))_(d)

with

R¹ and R³ independently representing an alkyl group containing from 1 to8 carbon atoms, R¹ preferably being a methyl group and R³ preferablybeing a propyl group,

a being between 0.05 and 0.5 and preferably between 0.15 and 0.4,

c being greater than zero, preferably between 0.15 and 0.4,

d being between 0.05 and 0.6, preferably between 0.2 and 0.6 oralternatively between 0.2 and 0.55,

a+b+c+d=1,

on condition that more than 40 mol % of the groups R³ of the siloxaneresin are propyl groups.

The siloxane resins that may be used according to the invention may beobtained via a process comprising the reaction of:

-   -   A) an MQ resin comprising at least 80 mol % of units (R¹        ₃SiO_(1/2))_(a) and (SiO_(4/2))_(d)        -   R¹ representing an alkyl group containing from 1 to 8 carbon            atoms, an aryl group, a carbinol group or an amino group,        -   a and d being greater than zero,        -   the ratio a/d being between 0.5 and 1.5;    -   and    -   B) a propyl resin T comprising at least 80 mol % of units        (R³SiO_(3/2))_(c),        -   R³ representing an alkyl group containing from 1 to 8 carbon            atoms, an aryl group, a carbinol group or an amino group,        -   c being greater than zero,    -   on condition that at least 40 mol % of the groups R³ are propyl        groups,        in which the mass ratio A/B is between 95/5 and 15/85 and        preferably the mass ratio A/B is 30/70.

Advantageously, the mass ratio A/B is between 95/5 and 15/85.Preferably, the ratio A/B is less than or equal to 70/30. Thesepreferred ratios have proven to afford comfortable deposits due to theabsence of percolation of the rigid particles of MQ resin in thedeposit.

The compositions according to the invention may be in various forms,especially in the form of a powder, an anhydrous dispersion, awater/oil, water/wax, oil/water, multiple or wax/water emulsion, or agel.

The compositions according to the invention are found to have very goodstaying-power and transfer-resistance properties while at the same timemaintaining a comfortable deposit, especially when it is applied to thelips.

The resins that may be used according to the invention are especiallythose described in patent application WO 2005/075 542, the content ofwhich is incorporated herein by reference.

According to a first embodiment, the composition according to theinvention is liquid.

According to a second embodiment, the composition according to theinvention is solid.

The term “solid” characterizes the state of the composition at roomtemperature (25° C.) and at atmospheric pressure (760 mmHg).

Preferably, the composition according to the invention has, when it issolid, a hardness of between 30 and 300 g, or even from 50 to 200 g.

Protocol for Measuring the Shear:

The measurement is performed according to the following protocol:

A sample of the composition under consideration is hot-cast into a stickmould 12.7 mm in diameter. The mould is then cooled in a freezer forabout one hour. The stick of lipstick is then stored at 20° C.

The hardness of the samples is measured after an interval of 24 hours.

The hardness of the samples of compositions of the invention, expressedin grams, is measured using a DFGS2 tensile testing machine sold by thecompany Indelco-Chatillon.

The hardness corresponds to the maximum shear force exerted by a rigidtungsten wire 250 μm in diameter, advancing at a rate of 100 mm/minute.

The technique described above is usually referred to as the “cheesewire” method.

Preferably, the composition according to the invention comprises lessthan 3% and better still less than 1% by weight of water relative to thetotal weight of the composition. More preferably, the composition istotally anhydrous. The term “anhydrous” especially means that water ispreferably not deliberately added to the composition, but may be presentin trace amount in the various compounds used in the composition.

According to another aspect, the present invention relates to a makeupand/or care process in which the composition as defined previously isapplied to keratin materials, and especially to the lips.

Film-Forming Polymer:

In the present invention, the term “film-forming polymer” means apolymer that is capable, by itself or in the presence of an auxiliaryfilm-forming agent, of forming a macroscopically continuous film thatadheres to keratin materials, and preferably a cohesive film, betterstill a film whose cohesion and mechanical properties are such that thesaid film can be isolated and manipulated individually, for example whenthe said film is prepared by pouring onto a non-stick surface such as aTeflon-coated or silicone-coated surface.

Block Ethylenic Polymer

According to a first embodiment of the invention, the film-formingpolymer present in the composition according to the invention is afilm-forming block ethylenic polymer (which is preferably essentiallylinear), which preferably comprises at least a first block and at leasta second block with different glass transition temperatures (Tg), thesaid first and second blocks being linked together via an intermediateblock comprising at least one constituent monomer of the first block andat least one constituent monomer of the second block.

The term “at least one block” means one or more blocks.

The term “block polymer” means a polymer comprising at least twodifferent blocks and preferably at least three different blocks.

Advantageously, the first and second blocks of the block polymer areadvantageously mutually incompatible.

Such polymers are described, for example, in documents EP 1 411 069 orWO 04/028 488. Patent application EP 1 411 069 describes the possibilityof preparing block polymers from acrylate monomers or methacrylatemonomers.

Preferably, according to this embodiment, the film-forming polymerpresent in the composition according to the invention is a blockpolymer, comprising at least a first block and at least a second block,characterized in that the first block is obtained from at least oneacrylate monomer of formula CH₂═CH—COOR₂ in which R₂ represents a C₄ toC₁₂ cycloalkyl group, and from at least one methacrylate monomer offormula CH₂═C(CH₃)—COOR₂ in which R′₂ represents a C₄ to C₁₂ cycloalkylgroup, and characterized in that the second block is obtained from anacrylic acid monomer and from at least one monomer with a glasstransition temperature of less than or equal to 20° C. Such polymers andthe process for preparing them are described, for example, in documentEP 1 882 709.

The first block and the second block of the polymer of the invention maybe advantageously mutually incompatible.

The term “mutually incompatible blocks” means that the blend formed froma polymer corresponding to the first block and from a polymercorresponding to the second block is not miscible in the polymerizationsolvent that is the majority amount by weight of the block polymer, atroom temperature (25° C.) and atmospheric pressure (10⁵ Pa), for apolymer blend content of greater than or equal to 5% by weight, relativeto the total weight of the blend and of the said polymerization solvent,it being understood that:

-   -   i) the said polymers are present in the blend in a content such        that the respective weight ratio ranges from 10/90 to 90/10, and        that    -   ii) each of the polymers corresponding to the first and second        blocks has an average (weight-average or number-average)        molecular mass equal to that of the block polymer ±15%.

In the case of a mixture of polymerization solvents, and should two ormore solvents be present in identical mass proportions, the said polymerblend is immiscible in at least one of them.

Needless to say, in the case of a polymerization performed in a singlesolvent, this solvent is the majority solvent.

The said first and second blocks may be advantageously linked togethervia an intermediate block comprising at least one constituent monomer ofthe first block and at least one constituent monomer of the secondblock.

The intermediate block is a block comprising at least one constituentmonomer of the first block and at least one constituent monomer of thesecond block of the polymer, which enables these blocks to be“compatibilized”.

Advantageously, the intermediate block comprising at least oneconstituent monomer of the first block and at least one constituentmonomer of the second block of the polymer is a random polymer.

Preferably, the intermediate block is derived essentially fromconstituent monomers of the first block and of the second block.

The term “essentially” means at least 85%, preferably at least 90%,better still 95% and even better still 100%.

Advantageously, the intermediate block has a glass transitiontemperature Tg that is between the glass transition temperatures of thefirst and second blocks.

The block polymer according to the invention is advantageously afilm-forming block ethylenic polymer.

The term “ethylenic polymer” means a polymer obtained by polymerizationof ethylenically unsaturated monomers.

The term “film-forming polymer” means a polymer that is capable offorming, by itself or in the presence of a film-forming auxiliary agent,a continuous film that adheres to a support, especially to keratinmaterials.

Preferentially, the polymer used in the composition according to theinvention comprises no silicon atoms in its backbone. The term“backbone” means the main chain of the polymer, as opposed to thependent side chains.

Preferably, the polymer according to the invention is not water-soluble,i.e. the polymer is not soluble in water or in a mixture of water and oflinear or branched lower monoalcohols containing from 2 to 5 carbonatoms, for instance ethanol, isopropanol or n-propanol, without pHmodification, at an active material content of at least 1% by weight, atroom temperature (25° C.).

Preferably, the polymer according to the invention is not an elastomer.

The term “non-elastomeric polymer” means a polymer which, when it issubjected to a constraint intended to pull it (for example by 30%relative to its initial length), does not return to a lengthsubstantially identical to its initial length when the constraintceases.

More specifically, the term “non-elastomeric polymer” denotes a polymerwith an instantaneous recovery R_(i)<50% and a delayed recoveryR_(2h)<70% after having been subjected to a 30% elongation. Preferably,R_(i) is <30% and R_(2h)<50%.

More specifically, the non-elastomeric nature of the polymer isdetermined according to the following protocol:

A polymer film is prepared by pouring a solution of the polymer in aTeflon-coated mould, followed by drying for 7 days in an environmentconditioned at 23±5° C. and 50±10% relative humidity.

A film about 100 μm thick is thus obtained, from which are cutrectangular specimens (for example using a punch) 15 mm wide and 80 mmlong.

This sample is subjected to a tensile stress using a machine sold underthe reference Zwick, under the same temperature and humidity conditionsas for the drying.

The specimens are pulled at a speed of 50 mm/min and the distancebetween the jaws is 50 mm, which corresponds to the initial length (l₀)of the specimen.

The instantaneous recovery R_(i) is determined in the following manner:

-   -   the specimen is pulled by 30% (ε_(max)), i.e. about 0.3 times        its initial length (1₀)    -   the constraint is released by applying a return speed equal to        the tensile speed, i.e. 50 mm/min, and the residual elongation        of the specimen is measured as a percentage, after returning to        zero constraint (ε_(i)).

The percentage instantaneous recovery (R_(i)) is given by the followingformula:

R _(i)=(ε_(max)−ε_(i))/(ε_(max))×100

To determine the delayed recovery, the percentage residual elongation ofthe specimen (ε_(2h)) is measured after 2 hours (2 hours after returningto zero stress load).

The percentage delayed recovery (R_(2h)) is given by the followingformula:

R _(2h)=(ε_(max)−ε_(2h))/(ε_(max))×100

Purely as a guide, a polymer according to one embodiment of theinvention has an instantaneous recovery R_(i) of 10% and a delayedrecovery R_(2h) of 30%.

The polydispersity index of the polymer of the invention isadvantageously greater than 2.

The polydispersity index I of the polymer is equal to the ratio of theweight-average mass Mw to the number-average mass Mn.

The weight-average molar mass (Mw) and number-average molar mass (Mn)are determined by gel permeation liquid chromatography (THF solvent,calibration curve established with linear polystyrene standards,refractometric detector).

The weight-average mass (Mw) of the polymer according to the inventionis preferably less than or equal to 300 000; it ranges, for example,from 35 000 to 200 000 and better still from 45 000 to 150 000 g/mol.

The number-average mass (Mn) of the polymer according to the inventionis preferably less than or equal to 70 000; it ranges, for example, from10 000 to 60 000 and better still from 12 000 to 50 000 g/mol.

Preferably, the polydispersity index of the polymer according to theinvention is advantageously greater than 2, for example ranging from 2to 9, preferably greater than or equal to 2.5, for example ranging from2.5 to 8, and better still greater than or equal to 2.8, especially from2.8 to 6.

The block polymer of the invention comprises at least a first block andat least a second block.

The first block is advantageously obtained from at least one acrylatemonomer of formula CH₂═CH—COOR₂ and from at least one methacrylatemonomer of formula CH₂═C(CH₃)—COOR₂ in which R₂ represents a C₄ to C₁₂cycloalkyl group. The monomers and the proportions thereof arepreferably chosen such that the glass transition temperature of thefirst block is greater than 20° C.

The second block is advantageously obtained from an acrylic acid monomerand from at least one monomer with a glass transition temperature ofless than or equal to 20° C.

The monomers and the proportions thereof are preferably chosen such thatthe glass transition temperature of the second block is less than orequal to 20° C.

The glass transition temperatures indicated for the first and secondblocks may be theoretical Tg values determined from the theoretical Tgvalues of the constituent monomers of each of the blocks, which may befound in a reference manual such as the Polymer Handbook, 3rd Edition,1989, John Wiley, according to the following relationship, known asFox's law:

${{1/{Tg}} = {\sum\limits_{i}\left( {{\overset{\_}{\omega}}_{i}/{Tg}_{i}} \right)}},$

ω _(i) being the mass fraction of the monomer i in the block underconsideration and Tg_(i) being the glass transition temperature of thehomopolymer of the monomer i.

Unless otherwise indicated, the Tg values indicated for the first andsecond blocks in the present patent application are theoretical Tgvalues.

The difference between the glass transition temperatures of the firstand second blocks is generally greater than 10° C., preferably greaterthan 20° C. and better still greater than 30° C.

In the present invention, the expression: “between . . . and . . . ” isintended to denote a range of values for which the limits mentioned areexcluded, and “from . . . to . . . ” and “ranging from . . . to . . . ”are intended to denote a range of values for which the limits areincluded.

First Block

The first block preferably has a Tg of greater than 20° C., for examplea Tg ranging from 20 to 170° C. and preferably greater than or equal to50° C., for example ranging from 50° C. to 160° C., especially rangingfrom 90° C. to 130° C.

According to one embodiment, the first block is obtained from at leastone acrylate monomer of formula CH₂═CH—COOR₂ in which R₂ represents a C₄to C₁₂ cycloalkyl group, and from at least one methacrylate monomer offormula CH₂═C(CH₃)—COOR′₂ in which R′₂ represents a C₄ to C₁₂ cycloalkylgroup.

The first block may be obtained exclusively from the said acrylatemonomer and from the said methacrylate monomer.

The acrylate monomer and the methacrylate monomer are preferably in massproportions of between 30/70 and 70/30, preferably between 40/50 and50/40 and especially of the order of 50/50.

The proportion of the first block advantageously ranges from 20% to 90%,better still from 30% to 80% and even better still from 60% to 80% byweight of the polymer.

According to one embodiment, the first block is obtained bypolymerization of isobornyl methacrylate and isobornyl acrylate.

The first block may also comprise:

-   -   (meth)acrylic acid, preferably acrylic acid,    -   tert-butyl acrylate,    -   the methacrylates of formula CH₂═C(CH₃)—COOR₁, in which R₁        represents a linear or branched unsubstituted alkyl group        containing from 1 to 4 carbon atoms, such as a methyl, ethyl,        propyl or isobutyl group,    -   the (meth)acrylamides of formula:

in which R₇ and R₈, which may be identical or different, each representa hydrogen atom or a linear or branched C₁ to C₁₂ alkyl group, such asan n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; orR₇ represents H and R₈ represents a 1,1-dimethyl-3-oxobutyl group,and R′ denotes H or methyl. Examples of monomers that may be mentionedinclude N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide,N,N-dimethylacrylamide and N,N-dibutylacrylamide,

-   -   and mixtures thereof.

Second Block

The second block advantageously has a glass transition temperature Tg ofless than or equal to 20° C., for example a Tg ranging from −100 to 20°C., preferably less than or equal to 15° C., especially ranging from−80° C. to 15° C. and better still less than or equal to 10° C., forexample ranging from −100° C. to 10° C., especially ranging from −30° C.to 10° C.

The second block is obtained from an acrylic acid monomer and fromanother monomer with a Tg of less than or equal to 20° C.

The monomer with a Tg of less than or equal to 20° C. is preferablychosen from the following monomers:

-   -   the acrylates of formula CH₂═CH—COOR₃,        R₃ representing a linear or branched, unsubstituted C₁-C₁₂ alkyl        group, with the exception of a tert-butyl group, in which is        (are) optionally intercalated one or more heteroatoms chosen        from O, N and S;    -   the methacrylates of formula CH₂═C(CH₃)—COOR₄,        R₄ representing a linear or branched, unsubstituted C₆-C₁₂ alkyl        group, in which is (are) optionally intercalated one or more        heteroatoms chosen from O, N and S;    -   vinyl esters of formula R₅—CO—O—CH═CH₂,        in which R₅ represents a linear or branched C₄-C₁₂ alkyl group;    -   (C₄-C₁₂ alkyl) vinyl ethers;    -   N—(C₄-C₁₂ alkyl)acrylamides, such as N-octylacrylamide;    -   and mixtures thereof.

The preferred monomers with a Tg of less than or equal to 20° C. areisobutyl acrylate and 2-ethylhexyl acrylate, or mixtures thereof in allproportions.

Each of the first and second blocks may contain in minor proportion atleast one constituent monomer of the other block.

Thus, the first block may contain at least one constituent monomer ofthe second block, and vice versa.

Each of the first and/or second blocks may comprise, in addition to themonomers indicated above, one or more other monomers known as additionalmonomers, which are different from the main monomers mentioned above.

The nature and amount of this or these additional monomer(s) are chosensuch that the block in which they are present has the desired glasstransition temperature.

This additional monomer is chosen, for example, from:

-   -   ethylenically unsaturated monomers comprising at least one        tertiary amine function, for instance 2-vinylpyridine,        4-vinylpyridine, dimethylaminoethyl methacrylate,        diethylaminoethyl methacrylate and        dimethylaminopropylmethacrylamide, and salts thereof,    -   methacrylates of formula CH₂═C(CH₃)—COOR₆,        in which R₆ represents a linear or branched alkyl group        containing from 1 to 4 carbon atoms, such as a methyl, ethyl,        propyl or isobutyl group, the said alkyl group being substituted        with one or more substituents chosen from hydroxyl groups (for        instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl        methacrylate) and halogen atoms (Cl, Br, I or F), such as        trifluoroethyl methacrylate,    -   methacrylates of formula CH₂═C(CH₃)—COOR₉,

R₉ representing a linear or branched C₆ to C₁₂ alkyl group in which oneor more heteroatoms chosen from O, N and S is (are) optionallyintercalated, the said alkyl group being substituted with one or moresubstituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I orF);

-   -   acrylates of formula CH₂═CHCOOR₁₀,

R₁₀ representing a linear or branched C₁ to C₁₂ alkyl group substitutedwith one or more substituents chosen from hydroxyl groups and halogenatoms (Cl, Br, I or F), such as 2-hydroxypropyl acrylate and2-hydroxyethyl acrylate, or R₁₀ represents a C₁ to C₁₂ alkyl-O-POE(polyoxyethylene) with repetition of the oxyethylene unit 5 to 30 times,for example methoxy-POE, or R₁₀ represents a polyoxyethylenated groupcomprising from 5 to 30 ethylene oxide units.

The additional monomer may represent 0.5% to 30% by weight relative tothe weight of the polymer. According to one embodiment, the polymer ofthe invention does not contain any additional monomer.

Preferably, the polymer of the invention comprises at least one of theisobornyl acrylate and isobornyl methacrylate monomers in the firstblock and isobutyl acrylate and acrylic acid monomers in the secondblock.

Preferably, the polymer comprises at least one of the isobornyl acrylateand isobornyl methacrylate monomers in equivalent weight proportion inthe first block and isobutyl acrylate and acrylic acid monomers in thesecond block.

Preferably, the polymer comprises at least isobornyl acrylate andisobornyl methacrylate monomers in equivalent weight proportion in thefirst block, and isobutyl acrylate and acrylic acid monomers in thesecond block, the first block representing 70% of the weight of thepolymer.

Preferably, the polymer comprises at least isobornyl acrylate andisobornyl methacrylate monomers in equivalent weight proportion in thefirst block, and isobutyl acrylate and acrylic acid monomers in thesecond block, the block with a Tg of greater than 20° C. representing70% of the weight of the polymer, and acrylic acid representing 5% ofthe weight of the polymer.

Vinyl Polymer Grafted with a Carbosiloxane Dendrimer

According to a second embodiment of the invention, the film-formingpolymer present in the composition according to the invention is a vinylpolymer comprising at least one carbosiloxane dendrimer-based unit.

The vinyl polymer may especially have a backbone and at least one sidechain, which comprises a carbosiloxane dendrimer structure. The term“carbosiloxane dendrimer structure” in the context of the presentinvention represents a structure with branched groups of high molecularmasses with high regularity in the radial direction starting from thesimple backbone. Such carbosiloxane dendrimer structures are describedin the form of a highly branched siloxane-silylalkylene copolymer in thelaid-open Japanese patent application Kokai 9-171 154.

The vinyl polymer contains carbosiloxane dendrimer-based units that maybe represented by the following general formula:

in which R¹ represents an aryl group or an alkyl group containing from 1to 10 carbon atoms, and X′ represents a silylalkyl group which, wheni=1, is represented by the formula:

in which R¹ is the same as defined above, R² represents an alkylenegroup containing from 2 to 10 carbon atoms, R³ represents an alkyl groupcontaining from 1 to 10 carbon atoms, X^(i+1) represents a hydrogenatom, an alkyl group containing from 1 to 10 carbon atoms, an aryl groupor the silylalkyl group defined above with i=i+1; i is an integer from 1to 10 which represents the generation of the said silylalkyl group, anda^(i) is an integer from 0 to 3; Y represents an organic group that maybe polymerized using radicals chosen from the group consisting of anorganic group that contains a methacrylic group or an acrylic group andthat is represented by the formulae:

in which R⁴ represents a hydrogen atom or an alkyl group, R⁵ representsan alkylene group containing from 1 to 10 carbon atoms, such as amethylene group, an ethylene group, a propylene group or a butylenegroup, the methylene group and the propylene group being preferred; and

an organic group that contains a styryl group and that is represented bythe formula:

in which R⁶ represents a hydrogen atom or an alkyl group, R⁷ representsan alkyl group containing from 1 to 10 carbon atoms, such as a methylgroup, an ethyl group, a propyl group or a butyl group, the methyl groupbeing preferred, R⁸ represents an alkylene group containing from 1 to 10carbon atoms, such as a methylene group, an ethylene group, a propylenegroup or a butylene group, the ethylene group being preferred, b is aninteger from 0 to 4, and c is 0 or 1 such that if c is 0, —(R⁸)_(c)—represents a bond,

R¹ represents an aryl group or an alkyl group containing from 1 to 10carbon atoms, in which the alkyl group is preferably represented by amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, an isopropyl group, an isobutyl group, a cyclopentyl group or acyclohexyl group, and in which the aryl group is preferably representedby a phenyl group and a naphthyl group, in which the methyl and phenylgroups are more particularly preferred, and the methyl group ispreferred among all.

The vinyl polymer that contains a carbosiloxane dendrimer structure maybe the product of polymerization of

(A) from 0 to 99.9 parts by weight of a monomer of vinyl type; and

(B) from 100 to 0.1 parts by weight of a carbosiloxane dendrimercontaining an organic group that may be polymerized using radicals,represented by the general formula:

in which Y represents an organic group that may be polymerized usingradicals, R¹ represents an aryl group or an alkyl group containing from1 to 10 carbon atoms, and X¹ represents a silylalkyl group which, wheni=1, is represented by the formula:

in which R¹ is the same as defined above, R² represents an alkylenegroup containing from 2 to 10 carbon atoms, R³ represents an alkyl groupcontaining from 1 to 10 carbon atoms, X^(i+1) represents a hydrogenatom, an alkyl group containing from 1 to 10 carbon atoms, an arylgroup, or the silylalkyl group defined above with i=i+1; i is an integerfrom 1 to 10 that represents the generation of the said silylalkylgroup, and a^(i) is an integer from 0 to 3; in which the said organicgroup that may be polymerized with radicals contained in the component(B) is chosen from the group consisting of an organic group thatcontains a methacrylic group or an acrylic group and that is representedby the formulae:

in which R⁴ represents a hydrogen atom or an alkyl group, R⁵ representsan alkylene group containing from 1 to 10 carbon atoms; and

an organic group that contains a styryl group and that is represented bythe formula:

in which R⁶ represents a hydrogen atom or an alkyl group, R⁷ representsan alkyl group containing from 1 to carbon atoms, R⁸ represents analkylene group containing from 1 to 10 carbon atoms, b is an integerfrom 0 to 4, and c is 0 or 1. When c is 0, —(R⁸)_(c)-represents a bond.

The monomer of vinyl type that is the component (A) in the vinyl polymeris a monomer of vinyl type that contains a radical-polymerizable vinylgroup. There is no particular limitation as regards the type of such amonomer. The following are examples of this type of vinyl monomer:methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,isopropyl methacrylate or a methacrylate of a lower alkyl analogue;glycidyl methacrylate; n-butyl methacrylate, isobutyl methacrylate,tert-butyl methacrylate, n-hexyl methacrylate, methacrylic acid,cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate,lauryl methacrylate, stearyl methacrylate or a higher-analoguemethacrylate; vinyl acetate, vinyl propionate or a vinyl ester of alower fatty acid analogue; vinyl caproate, vinyl 2-ethylhexoate, vinyllaurate, vinyl stearate or an ester of a higher fatty acid analogue;styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate,vinyl-pyrrolidone or similar vinylaromatic monomers; methacrylamide,N-methylolmethacrylamide, N-methoxy-methylmethacrylamide,isobutoxymethoxymethacrylamide, N,N-dimethylmethacrylamide or similarmonomers of vinyl type containing amide groups; hydroxyethylmethacrylate, hydroxypropyl methacrylate or similar monomers of vinyltype containing hydroxyl groups; methacrylic acid, itaconic acid,crotonic acid, fumaric acid, maleic acid or similar monomers of vinyltype containing a carboxylic acid group; tetrahydrofurfurylmethacrylate, butoxyethyl methacrylate, ethoxydiethylene glycolmethacrylate, polyethylene glycol methacrylate, polypropylene glycolmonomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether,2-ethylhexyl vinyl ether or a similar monomer of vinyl type with etherbonds; methacryloxypropyl-trimethoxysilane, polydimethylsiloxanecontaining a methacrylic group on one of its molecular ends,polydimethylsiloxane containing a styryl group on one of its molecularends, or a similar silicone compound containing unsaturated groups;butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile;dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid;methacryl glycidyl ether; an organic salt of an amine, an ammonium salt,and an alkali metal salt of methacrylic acid, of itaconic acid, ofcrotonic acid, of maleic acid or of fumaric acid; aradical-polymerizable unsaturated monomer containing a sulfonic acidgroup such as a styrenesulfonic acid group; a quaternary ammonium saltderived from methacrylic acid, such as2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and amethacrylic acid ester of an alcohol containing a tertiary amine group,such as a methacrylic acid ester of diethylamine.

Multifunctional monomers of vinyl type may also be used. The followingrepresent examples of such compounds: trimethylolpropanetrimethacrylate, pentaerythrityl trimethacrylate, ethylene glycoldimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycoldimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol dimethacrylate,trimethylolpropane-trioxyethyl methacrylate,tris(2-hydroxyethyl)-isocyanurate dimethacrylate,tris(2-hydroxyethyl)-isocyanurate trimethacrylate, polydimethylsiloxanecapped with styryl groups containing divinylbenzene groups on both ends,or similar silicone compounds containing unsaturated groups.

The carbosiloxane dendrimer, which is the component (B), is representedby the following formula:

The following represent the preferred examples of radical-polymerizableorganic group Y: an acryloxymethyl group, a 3-acryloxypropyl group, amethacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenylgroup, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a2-(3-vinyl-phenyl)ethyl group, a vinyl group, an allyl group, amethallyl group and a 5-hexenyl group.

R¹ represents an alkyl group or an aryl group containing from 1 to 10carbon atoms, in which the alkyl group may be a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, an isopropylgroup, an isobutyl group, a cyclopentyl group or a cyclohexyl group; andthe aryl group may be a phenyl group or a naphthyl group. The methyl andphenyl groups are particularly preferred, the methyl group beingpreferred among all. X¹ represents a silylalkyl group that isrepresented by the following formula, when i is equal to 1:

in which R² represents an alkylene group containing from 2 to 10 carbonatoms, such as an ethylene group, a propylene group, a butylene group, ahexylene group or a similar linear alkylene group; a methylmethylenegroup, a methylethylene group, a 1-methylpentylene group, a1,4-dimethylbutylene group or a similar branched alkylene group. Theethylene, methylethylene, hexylene, 1-methylpentylene and1,4-dimethylbutylene groups are preferred among all. R³ represents analkyl group containing from 1 to 10 carbon atoms, such as methyl, ethyl,propyl, butyl and isopropyl groups. R¹ is the same as defined above.X^(i+1) represents a hydrogen atom, an alkyl group containing from 1 to10 carbon atoms, an aryl group or the silylalkyl group with i=i+1. a^(i)is an integer from 0 to 3, and i is an integer from 1 to 10 thatindicates the generation number, which represents the number ofrepetitions of the silylalkyl group.

For example, when the generation number is equal to 1, the carbosiloxanedendrimer may be represented by the first general formula shown below,in which Y, R¹, R² and R³ are the same as defined above, R¹² representsa hydrogen atom or is identical to R¹; a¹ is identical to a^(i).Preferably, the mean total number of groups OR³ in a molecule is withinthe range from 0 to 7. When the generation number is equal to 2, thecarbosiloxane dendrimer may be represented by the second general formulashown below, in which Y, R¹, R², R³ and R¹² are the same as definedabove; a¹ and a² represent the a^(i) of the indicated generation.Preferably, the mean total number of groups OR³ in a molecule is withinthe range from 0 to 25. When the generation number is equal to 3, thecarbosiloxane dendrimer is represented by the third general formulashown below, in which Y, R², R³ and R¹² are the same as defined above;a¹, a² and a³ represent the a^(i) of the indicated generation.Preferably, the total mean number of groups OR³ in a molecule is withinthe range from 0 to 79.

A carbosiloxane dendrimer that contains a radical-polymerizable organicgroup may be represented by the following mean structural formulae:

The carbosiloxane dendrimer may be manufactured according to the processfor manufacturing a branched silalkylene siloxane described in Japanesepatent application Hei 9-171 154. For example, it may be produced bysubjecting an organosilicon compound containing a hydrogen atom linkedto a silicon atom, represented by the following general formula:

and an organosilicon compound containing an alkenyl group, to ahydrosilylation reaction. In the above formula, the organosiliconcompound may be represented by3-methacryloxypropyltris(dimethyl-siloxy)silane,3-acryloxypropyltris(dimethylsiloxy)-silane and4-vinylphenyltris(dimethylsiloxy)silane. The organosilicon compound thatcontains an alkenyl group may be represented byvinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane,and 5-hexenyl-tris(trimethylsiloxy)silane. The hydrosilylation reactionis performed in the presence of a chloroplatinic acid, a complex ofvinylsiloxane and of platinum, or a similar transition metal catalyst.

In the vinyl polymer that contains a dendrimer structure, thepolymerization ratio between the components (A) and (B), in terms of theweight ratio between (A) and (B), may be within the range from 0/100 to99.9/0.1 and preferably within the range from 1/99 to 99/1. A ratiobetween the components (A) and (B) of 0/100 means that the compoundbecomes a homopolymer of component (B).

The vinyl polymer contains a carbosiloxane dendrimer structure and thispolymer may be obtained by copolymerization of the components (A) and(B), or by polymerization of the component (B) alone. The polymerizationmay be a free-radical polymerization or an ionic polymerization, butfree-radical polymerization is preferred. The polymerization may beperformed by bringing about a reaction between the components (A) and(B) in a solution for a period of from 3 to 20 hours in the presence ofa radical initiator at a temperature of from 50° C. to 150° C. Asuitable solvent for this purpose is hexane, octane, decane, cyclohexaneor a similar aliphatic hydrocarbon; benzene, toluene, xylene or asimilar aromatic hydrocarbon; diethyl ether, dibutyl ether,tetrahydrofuran, dioxane or similar ethers; acetone, methyl ethylketone, methyl isobutyl ketone, diisobutyl ketone or similar ketones;methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate orsimilar esters; methanol, ethanol, isopropanol, butanol or similaralcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,hexamethyldisiloxane, octamethyltrisiloxane or a similar organosiloxaneoligomer. A radical initiator may be any compound known in the art forstandard free-radical polymerization reactions. The specific examples ofsuch radical initiators are 2,2′-azobis(isobutyronitrile),2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile) or similar compounds of azobistype; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate,tert-butyl peroxy-2-ethylhexanoate or a similar organic peroxide. Theseradical initiators may be used alone or in a combination of two or more.The radical initiators may be used in an amount of from 0.1 to 5 partsby weight per 100 parts by weight of the components (A) and (B). Achain-transfer agent may be added. The chain-transfer agent may be2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan,3-mercaptopropyltrimethoxysilane, a polydimethyl-siloxane containing amercaptopropyl group or a similar compound of mercapto type; methylenechloride, chloroform, carbon tetrachloride, butyl bromide,3-chloropropyltrimethoxysilane or a similar halogenated compound. In themanufacture of the polymer of vinyl type, after the polymerization, theresidual unreacted vinyl monomer may be removed under conditions ofheating under vacuum.

To facilitate the preparation of the mixture of the starting material ofcosmetic products, the number-average molecular mass of the vinylpolymer containing a carbosiloxane dendrimer may be chosen within therange between 3000 and 2 000 000 and preferably between 5000 and 800000. It may be a liquid, a gum, a paste, a solid, a powder or any otherform. The preferred forms are solutions consisting of the dilution of adispersion or of a powder in solvents.

The vinyl polymer may be a dispersion of a polymer of vinyl type havinga carbosiloxane dendrimer structure in its side molecular chain, in aliquid such as a silicone oil, an organic oil, an alcohol or water.

The vinyl polymer having a carbosiloxane dendrimer structure in its sidemolecular chain, in this embodiment, is the same as that describedabove. The liquid may be a silicone oil, an organic oil, an alcohol orwater. The silicone oil may be a dimethylpolysiloxane with the twomolecular ends capped with trimethylsiloxy groups, a copolymer ofmethylphenylsiloxane and of dimethylsiloxane having the two molecularends capped with trimethylsiloxy groups, a copolymer ofmethyl-3,3,3-trifluoropropylsiloxane and of dimethylsiloxane having thetwo molecular ends capped with trimethylsiloxy groups, or similarunreactive linear silicone oils, and also hexamethyl-cyclotrisiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclo-hexasiloxane or a similar cyclic compound. In additionto the unreactive silicone oils, modified polysiloxanes containingfunctional groups such as silanol groups, amino groups and polyethergroups on the ends or within the side molecular chains may be used.

The organic oils may be liquid paraffin, isoparaffin, hexyl laurate,isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecylmyristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate,decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate,lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol,avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil,sunflower oil, soybean oil, camellia oil, squalane, castor oil, minkoil, cottonseed oil, coconut oil, egg yolk oil, beef tallow, lard,polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate or asimilar glycol ester oil; triglyceryl isostearate, the triglyceride of afatty acid of coconut oil, or a similar oil of a polyhydric alcoholester; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether or asimilar polyoxyalkylene ether.

The alcohol may be any type that is suitable for use in combination witha cosmetic product starting material. For example, it may be methanol,ethanol, butanol, isopropanol or similar lower alcohols. A solution or adispersion of the alcohol should have a viscosity within the range from10 to 10⁹ mPa at 25° C. To improve the sensory use properties in acosmetic product, the viscosity should be within the range from 100 to5×10⁸ mPa·s.

The solutions and dispersions may be readily prepared by mixing thevinyl polymer having a carbosiloxane dendrimer structure with a siliconeoil, an organic oil, an alcohol or water. The liquids may be present inthe step of polymerization of the polymer of vinyl type having acarbosiloxane dendrimer structure. In this case, the unreacted residualvinyl monomer should be completely removed by heat treatment of thesolution or dispersion under atmospheric pressure or reduced pressure.In the case of a dispersion, the dispersity of the polymer of vinyl typemay be improved by adding a surfactant. Such an agent may behexyl-benzenesulfonic acid, octylbenzenesulfonic acid,decylbenzenesulfonic acid, dodecylbenzenesulfonic acid,cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionicsurfactants of the sodium salts of these acids; octyltrimethylammoniumhydroxide, dodecyltrimethylammonium hydroxide,hexadecyltrimethyl-ammonium hydroxide, octyldimethylbenzylammoniumhydroxide, decyldimethylbenzylammonium hydroxide,dioctadecyldimethylammonium hydroxide, beef tallow-trimethylammoniumhydroxide, coconut oil-trimethylammonium hydroxide, or a similarcationic surfactant; a polyoxyalkylene alkyl ether, apolyoxyalkylenealkylphenol, a polyoxyalkylene alkyl ester, the sorbitolester of polyoxyalkylene, polyethylene glycol, polypropylene glycol, anethylene oxide additive of diethylene glycol trimethylnonanol, andnonionic surfactants of polyester type, and also mixtures. In addition,the solvents and dispersions may be combined with iron oxide suitablefor use with cosmetic products, or a similar pigment, and also zincoxide, titanium oxide, silicon oxide, mica, talc or similar mineraloxides in powder form. In the dispersion, a mean particle diameter ofthe polymer of vinyl type may be within a range of between 0.001 and 100microns and preferably between 0.01 and 50 microns. The reason for thisis that, outside the recommended range, a cosmetic product mixed withthe emulsion will not have a nice enough feel on the skin or to thetouch, or sufficient spreading properties or a pleasant feel.

The vinyl polymer contained in the dispersion or the solution may have aconcentration in the range between 0.1% and 95% by weight and preferablybetween 5% and 85% by weight. However, to facilitate the handling andthe preparation of the mixture, the range should preferably be between10% and 75% by weight.

The vinyl polymer may be one of the polymers described in the examplesof patent application EP 0 963 751 or, for example, the productTIB-4-200 sold by Dow Corning.

According to one embodiment, the vinyl polymer also comprises at leastone organofluorine group.

Structures in which the polymerized vinyl units constitute the backboneand carbosiloxane dendritic structures and also organofluorine groupsare attached to side chains are particularly preferred.

The organofluorine groups may be obtained by replacing with fluorineatoms all or some of the hydrogen atoms of methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl,cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, hexadecyl and octadecyl groups and other alkyl groups of 1to 20 carbon atoms, and also alkyloxyalkylene groups of 6 to 22 carbonatoms.

The groups represented by the formula: —(CH₂)_(x)—(CF₂)_(y)—R¹³ aresuggested as examples of fluoroalkyl groups obtained by substitutingfluorine atoms for hydrogen atoms of alkyl groups. In the formula, theindex “x” is 0, 1, 2 or 3 and “y” is an integer from 1 to 20. R¹³ is anatom or a group chosen from a hydrogen atom, a fluorine atom, —CH(CF₃)₂—and CF(CF₃)₂. Such fluorine-substituted alkyl groups are exemplified bylinear or branched polyfluoroalkyl or perfluoroalkyl groups representedby the formulae presented below.

—CF₃, —C₂F₅, -nC₃F₇, —CF (CF₃)₂, -nC₄F₉, CF₂CF(CF₃)₂,-nC₅F₁₁, -nC₆F₁₃,-nC₈F₁₇, —CH₂CF₃, —CH(CF₃)₂, CH₂CH(CF₃)₂—CH₂(CF₂)₂F, —CH₂(CF₂)₃F,—CH₂(CF₂)₄F, —CH₂(CF₂)₆F, —CH₂(CF₂)₈F, —CH₂CH₂CF₃, —CH₂CH₂(CF₂)₂F,—CH₂CH₂(CF₂)₃F, —CH₂CH₂(CF₂)₄F, —CH₂CH₂(CF₂)₆F, —CH₂CH₂(CF₂)₈F,—CH₂CH₂(CF₂)₁₀F, —CH₂CH₂(CF₂)₁₂F, —CH₂CH₂(CF₂)₁₄F, —CH₂CH₂(CF₂)₁₆F,—CH₂CH₂CH₂CF₃, —CH₂CH₂CH₂(CF₂)₂F, —CH₂CH₂CH₂(CF₂)₂H, —CH₂(CF₂)₄H, and—CH₂CH₂(CF₂)₃H.

The groups represented by —CH₂CH₂— (CF₂)_(m)—CFR¹⁴—[OCF₂CF(CF₃)]_(n)—OC₃F₇ are suggested as fluoroalkyloxyfluoroalkylene groupsobtained by substituting fluorine atoms for hydrogen atoms ofalkyloxyalkylene groups. In the formula, the index “m” is 0 or 1, “n” is0, 1, 2, 3, 4 or 5, and R¹⁴ is a fluorine atom CF₃. Suchfluoroalkyloxyfluoroalkylene groups are exemplified by theperfluoroalkyloxy-fluoroalkylene groups represented by the formulaepresented below:

—CH₂CH₂CF(CF₃)—[OCF₂CF(CF₃)]_(n)—OC₃F₇,—CH₂CH₂CF₂CF₂—[OCF₂CF(CF₃)]_(n)—OC₃F₇.

The number-average molecular weight of the vinyl polymer used in thepresent invention may be between 3000 and 2 000 000 and more preferablybetween 5000 and 800 000.

This type of fluorinated vinyl polymer may be obtained by addition

-   -   of a vinyl monomer (B) not containing any organofluorine groups        in the molecule    -   to a vinyl monomer containing organofluorine groups in the        molecule (A), and    -   a carbosiloxane dendrimer (C) containing radical-polymerizable        organic groups represented by the general formula (III):

in which Y is a radical-polymerizable organic group and R¹ and X^(i) areas above, and by subjecting them to a copolymerization.

The vinyl monomers (A) containing organofluorine groups in the moleculeare preferably monomers represented by the general formula:—(CH₂)═CR¹⁵COOR^(f). In the formula, R¹⁵ is a hydrogen atom or a methylgroup and R^(f) is an organofluorine group exemplified by thefluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above. Thecompounds represented by the formulae presented below are suggested asspecific examples of the component (A). In the formulae presented below“z” is an integer from 1 to 4.

CH₂═CCH₃COO—CF₃. CH₂═CCH₃COO—C₂F₅. CH₂═CCH₃COO-nC₃F₇ CH₂CCH₃COO—CF(CF₃)₂. CH₂═CCH₃COO-nC₄F₉. CH₂═CCH₃COO—CF₂CF (CF₃)₂.CH₂═CCH₃COO-nC₅F₁₁. CH₂═CCH₃COO-nC₆F₁₃. CH₂═CCH₃COO-nC₈F₁₇.CH₂═CCH₃COO—CH₂CF₃. CH₂═CCH₃COO—CH(CF₃)₂. CH₂═CCH₃COO—CH₂CH(CF₃)₂.CH₂═CCH₃COO—CH₂(CF₂)₂F. CH₂═CCH₃COO—CH₂(CF₂)₃F. CH₂═CCH₃COO—CH₂(CF₂)₄F.CH₂═CCH₃COO—CH₂(CF₂)₆F. CH₂═CCH₃COO—CH₂(CF₂)₈F. CH₂═CCH₃COO—CH₂CH₂CF₃.CH₂═CCH₃COO—CH₂CH₂(CF₂)₂F. CH₂═CCH₃COO—CH₂CH₂(CF₂)₃F.CH₂═CCH₃COO—CH₂CH₂(CF₂)₄F. CH₂═CCH₃COO—CH₂CH₂(CF₂)₆F.CH₂═CCH₃COO—CH₂CH₂(CF₂)₈F. CH₂═CCH₃COO—CH₂CH₂(CF₂)₁₀F.CH₂═CCH₃COO—CH₂CH₂(CF₂)₁₂F. CH₂═CCH₃COO—CH₂CH₂(CF₂)₁₄F.CH₂═CCH₃COO—CH₂CH₂(CF₂)₁₆F. CH₂═CCH₃COO—CH₂CH₂CH₂CF₃.CH₂═CCH₃COO—CH₂CH₂CH₂(CF₂)₂F. CH₂ CCH₃COO—CH₂CH₂CH₂(CF₂)₂H.CH₂═CCH₃COO—CH₂(CF₂)₄H. CH₂═CCH₃COO—CH₂CH₂(CF₂)₃H. CH₂═CCH₃COO—CH₂CH₂CF(CF₃)—[OCF₂CF(CF₃)]_(z)—OC₃F₇. CH₂═CCH₃COO—CH₂CH₂CF₂CF₂[OCF₂CF(CF₃)]_(z)—OC₃F₇. CH₂═CHCOO—CF₃. CH₂═CHCOO—C₂F₅. CH₂═CHCOO-nC₃F₇.CH₂═CHCOO—CF (CF₃)₂. CH₂═CHCOO-nC₄F₉. CH₂═CHCOO—CF₂CF (CF₃)₂.CH₂═CHCOO-nC₅F₁₁. CH₂═CHCOO-nC₆F₁₃. CH₂═CHCOO-nC₈F₁₇. CH₂═CHCOO—CH₂CF₃.CH₂═CHCOO—CH(CF₃)₂. CH₂═CHCOO—CH₂CH(CF₃)₂. CH₂═CHCOO—CH₂(CF₂)₂F.CH₂═CHCOO—CH₂(CF₂)₃F. CH₂═CHCOO—CH₂(CF₂)₄F. CH₂═CHCOO—CH₂(CF₂)₆F.CH₂═CHCOO—CH₂(CF₂)₈F. CH₂═CHCOO—CH₂CH₂CF₃. CH₂═CHCOO—CH₂CH₂(CF₂)₂F.CH₂═CHCOO—CH₂CH₂(CF₂)₃F. CH₂═CHCOO—CH₂CH₂(CF₂)₄F.CH₂═CHCOO—CH₂CH₂(CF₂)₆F. CH₂═CHCOO—CH₂CH₂(CF₂).CH₂═CHCOO—CH₂CH₂(CF₂)₁₀F. CH₂═CHCOO—CH₂CH₂(CF₂)₁₂F.CH₂═CHCOO—CH₂CH₂(CF₂)₁₄F. CH₂═CHCOO—CH₂CH₂(CF₂)₁₆F.CH₂═CHCOO—CH₂CH₂CH₂CF₃. CH₂═CHCOO—CH₂CH₂CH₂(CF₂)₂F.CH₂═CHCOO—CH₂CH₂CH₂(CF)₂H. CH₂═CHCOO—CH₂(CF₂)₄H.CH₂═CHCOO—CH₂CH₂(CF₂)₃H.CH₂═CHCOO—CH₂CH₂CF(CF₃)—[OCF₂CF(CF₃)]_(z)—OC₃F₇.CH₂═CHCOO—CH₂CH₂CF₂CF₂—[OCF₂CF (CF₃)]_(z)—OC₃F₇.

Among these, the vinyl polymers represented by the formulae presentedbelow are preferable:

CH₂═CHCOO—CH₂CH₂(CF₂)₆F. CH₂═CHCOO—CH₂CH₂(CF₂)CH₂═CCH₃COO—CH₂CH₂(CF₂)₆F. CH₂═CCH₃COO—CH₂CH₂(CF₂)₈F. CH₂═CHCOO—CH₂CF₃.CH₂═CCH₃COO—CH₂CF₃

The vinyl polymers represented by the formulae presented below areparticularly preferable.

CH₂═CHCOO—CH₂CF₃. CH₂═CCH₃COO—CH₂CF₃.

The vinyl monomers (B) not containing any organofluorine groups in themolecule may be any monomer containing radical-polymerizable vinylgroups illustrated, for example, by methyl acrylate, methylmethacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate,n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, andother lower alkyl acrylates or methacrylates; glycidyl acrylate,glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutylacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butylmethacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-hexyl acrylate,n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octylmethacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate,stearyl methacrylate, and other higher acrylates and methacrylates;vinyl acetate, vinyl propionate and other lower fatty acid vinyl esters;vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate,vinyl stearate, and other higher fatty acid esters; styrene,vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethylacrylate, phenoxyethyl methacrylate, vinylpyrrolidone, and othervinylaromatic monomers; dimethylaminoethyl acrylate, dimethylaminoethylmethacrylate, diethylaminoethyl acrylate, diethylaminoethylmethacrylate, and other aminovinyl monomers, acrylamide, methacrylamide,N-methylolacrylamide, N-methylolmethacrylamide,N-methoxymethylacrylamide, N-methoxymethyl-methacrylamide,isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide,N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and other vinylamidemonomers; hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylic acidhydroxypropyl alcohol, methacrylic acid hydroxypropyl alcohol, and otherhydroxyvinyl monomers; acrylic acid, methacrylic acid, itaconic acid,crotonic acid, fumaric acid, maleic acid, and other vinylcarboxylic acidmonomers; tetra-hydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate,butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene glycolacrylate, ethoxy-diethylene glycol methacrylate, polyethylene glycolacrylate, polyethylene glycol methacrylate, polypropylene glycolmonoacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinylether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other vinylmonomers containing an ether bond; acryloxypropyl-trimethoxysilane,methacryloxypropyltrimethoxysilane, polydimethylsiloxanes containingacryl or methacryl groups at one of the ends, polydimethylsiloxanescontaining alkenylaryl groups at one of the ends and other siliconecompounds containing unsaturated groups; butadiene; vinyl chloride;vinylidene chloride, acrylonitrile, methacrylonitrile; dibutyl fumarate;maleic anhydride; dodecylsuccinic anhydride; acryl glycidyl ether,methacryl glycidyl ether, 3,4-epoxy-cyclohexylmethyl acrylate,3,4-epoxycyclohexylmethyl methacrylate, alkali metal salts, ammoniumsalts and organic amine salts of acrylic acid, of methacrylic acid, ofitaconic acid, of crotonic acid, of fumaric acid, of maleic acid and ofother radical-polymerizable unsaturated carboxylic acids,radical-polymerizable unsaturated monomers containing sulfonic acidgroups, such as styrene sulfonic acid and also the alkali metal saltsthereof, the ammonium salts thereof and the organic amine salts thereof;the quaternary ammonium salts derived from acrylic acid or methacrylicacid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride,methacrylic acid esters of a tertiary amine alcohol, such as thediethylamine ester of methacrylic acid and quaternary ammonium saltsthereof.

In addition, it is also possible to use as vinyl monomers (B) thepolyfunctional vinyl monomers illustrated, for example, bytrimethylolpropane triacrylate, trimethylolpropane trimethacrylate,pentaerythrityl triacrylate, pentaerythrityl trimethacrylate, ethyleneglycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycoldiacrylate, tetraethylene glycol dimethacrylate, polyethylene glycoldiacrylate, polyethylene glycol dimethacrylate, 1,4-butanedioldiacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate,1,6-hexane-diol dimethacrylate, neopentyl glycol diacrylate, neopentylglycol dimethacrylate, trimethylolpropane-trioxyethyl acrylate,trimethylolpropanetrioxyethyl methacrylate,tris(2-hydroxyethyl)isocyanurate diacrylate,tris(2-hydroxyethyl)isocyanurate dimethacrylate,tris(2-hydroxyethyl)isocyanurate triacrylate,tris(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxanein which the two ends of the molecular chain are blocked withalkenylaryl groups, and other silicone compounds containing unsaturatedgroups.

As regards the ratio mentioned above in which the component (A) and thecomponent (B) are copolymerized, the weight ratio of compound (A) tocompound (B) should be within the range from 0.1:99.9 to 100:0 andpreferably within the range 1:99 to 100:0.

The carbosiloxane dendrimer (C) is represented by the general formula(III) indicated above. In formula (III), Y is a radical-polymerizableorganic group, the type of which is not subject to any speciallimitations provided that it is an organic group capable of undergoing aradical addition reaction. Organic groups containing acryl andmethacryl, organic groups containing alkenylaryl, or alkenyl groups of 2to 10 carbon atoms represented by the general formulae presented beloware suggested as specific examples.

In the formulae, R⁴ and R⁶ are hydrogen atoms or methyl groups, R⁵ andR⁸ are alkylene groups of 1 to 10 carbon atoms, and R⁷ is an alkyl groupof 1 to 10 carbon atoms. The index “b” is an integer from 0 to 4 and “c”is 0 or 1. Acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl,3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl,4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl,2-(3-vinylphenyl)enyl, vinyl, allyl, methallyl, and 5-hexenyl aresuggested as examples of such radical-polymerizable organic groups. Theindex “i” in formula (II), which is an integer from 1 to 10, is thenumber of generations of the said silylalkyl group, in other words thenumber of times that the silylalkyl group is repeated. Thus, thecarbosiloxane dendrimer of this component with a generation number of 1is represented by the general formula:

(in which Y, R¹, R² and R³ are as above and R¹² is a hydrogen atom orsuch as R¹ described above. The index “a¹” is an integer from 0 to 3,the total mean of “a¹” per molecule being from 0 to 7). Thecarbosiloxane dendrimers of this component with a generation number of 2are represented by the general formula:

(in which Y, R¹, R², R³ and R¹² are as above and the indices “a¹” and“a²” are integers from 0 to 3, the total mean of “a¹” and of “a²” permolecule being from 0 to 25).

The carbosiloxane dendrimers of this component with a generation numberof 3 are represented by the general formula:

(in which Y, R¹, R², R³ and R¹² are as above and the indices “a¹” and“a²” and “a³” are integers from 0 to 3, the total mean of “a¹”, “a²” and“a³” per molecule being from 0 to 79).

The component (C) is illustrated by carbosiloxane dendrimers representedby formulae of mean composition represented below.

The carbosiloxane dendrimers of the component (C) may be prepared usingthe process for preparing siloxane/silylalkylene branched copolymersdescribed in document EP 1 055 674. For example, they may be prepared bysubjecting organic alkenyl silicones and silicone compounds comprisinghydrogen atoms linked to silicon, represented by the general formula:

(in which R¹ and Y are as above) to a hydrosilylation reaction. Forexample, 3-methacryloxypropyltris(dimethylsiloxy)silane,3-acryloxypropyltris(dimethylsiloxy)silane and4-vinylphenyltris(dimethylsiloxy)silane are used as silicon compoundsrepresented by the above formula. Vinyltris(trimethylsiloxy)silane,vinyltris(dimethyl-phenylsiloxy)silane and5-hexenyltris(trimethylsiloxy)-silane are used as organosilicon alkenylcompounds. In addition, it is preferable to perform the hydrosilylationreaction in the presence of a transition metal catalyst such aschloroplatinic acid and the platinum/vinylsiloxane complex.

The copolymerization ratio of the component (C), in terms of its weightratio relative to the total weight of compounds (A) and (B) should bewithin the range from 0.1:99.9 to 99.9:0.1, preferably within the rangefrom 1:99 to 99:1 and even more preferably within the range from 5:95 to95:5.

Amino groups may be introduced into the side chains of the vinyl polymerusing, included in the component (B), vinyl monomers containing aminogroups, such as dimethylaminoethyl acrylate, dimethylaminoethylmethacrylate, diethylaminoethyl acrylate and diethyl-aminoethylmethacrylate, followed by performing a modification with potassiumacetate monochloride, ammonium acetate monochloride, theaminomethylpropanol salt of monochloroacetic acid, the triethanolaminesalt of monobromoacetic acid, sodium monochloropropionate, and otheralkali metal salts of halogenated fatty acids; otherwise, carboxylicacid groups may be introduced into the side chains of the vinyl polymerusing, included in the component (B), vinyl monomers containingcarboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid,crotonic acid, fumaric acid and maleic acid, and the like, followed byneutralizing the product with triethylamine, diethylamine,triethanolamine and other amines.

The fluorinated vinyl polymer may be one of the polymers described inthe examples of patent application WO 03/045337 or, for example, theproduct TIB-4-100 sold by Dow Corning.

The vinyl polymer may be present in a content ranging from 0.1% to 70%by weight, relative to the total weight of the composition, preferablyranging from 0.5% to 50% by weight, preferentially ranging from 1% to40% by weight and more preferably ranging from 5% to 15% by weight.

The vinyl polymer may be present in the composition in a proportion ofat least 3% by weight in the composition, preferably between 5% and 25%by weight, more preferably between 5% and 15% by weight and especiallyabout 10% by weight.

Polymer in Dispersion

According to a third embodiment of the invention, the film-formingpolymer present in the composition according to the invention is adispersion of homopolymer particles or of acrylic or vinyl radicalcopolymers dispersed in the liquid fatty phase of the composition.

According to the invention, the polymer in the form of particlesdispersed in the volatile liquid fatty phase is a solid that isinsoluble in the liquid fatty phase of the composition even at itssoftening point, unlike a wax even of polymeric origin, which is itselfsoluble in the liquid organic phase (or fatty phase) at its meltingpoint.

The composition according to the invention advantageously comprises atleast one stable dispersion of generally spherical polymer particles ofone or more polymers, in a volatile liquid fatty phase. Thesedispersions may especially be in the form of polymer nanoparticles instable dispersion in the said liquid organic phase. The nanoparticlespreferably have a mean size of between 5 and 800 nm and better stillbetween and 500 nm. However, it is possible to obtain polymer particlesranging up to 1 μm in size.

Preferably, the polymer particles in dispersion are insoluble inwater-soluble alcohols, for instance ethanol.

The polymers in dispersion that may be used in the composition of theinvention preferably have a molecular weight of about from 2000 to 10000 000 g/mol and a Tg of from −100° C. to 300° C., better still from−50° C. to 100° C. and preferably from −10° C. to 50° C.

It is possible to use film-forming polymers preferably having a low Tg,of less than or equal to skin temperature and especially less than orequal to 40° C.

Preferably, the polymer used is film-forming, i.e. it is capable offorming an isolable film, by itself or in combination with aplasticizer. It is, however, possible to use a non-film-forming polymer.

The term “non-film-forming polymer” means a polymer that is incapable offorming an isolable film by itself. This polymer can, in combinationwith a non-volatile compound of the oil type, form a continuous, uniformdeposit on the skin and/or the lips.

Among the film-forming polymers that may be mentioned are acrylic orvinyl free-radical homopolymers or copolymers, preferably with a Tg ofless than or equal to 40° C. and especially ranging from −10° C. to 30°C., used alone or as a mixture.

Among the non-film-forming polymers that may be mentioned are optionallycrosslinked vinyl or acrylic free-radical homopolymers or copolymerspreferably with a Tg of greater than 40° C. and especially ranging from45° C. to 150° C., used alone or as a mixture.

The term “free-radical polymer” means a polymer obtained bypolymerization of unsaturated and especially ethylenic monomers, eachmonomer being capable of homopolymerizing (unlike polycondensates). Thefree-radical polymers may especially be vinyl polymers or copolymers,especially acrylic polymers.

The acrylic polymers may result from the polymerization of ethylenicallyunsaturated monomers containing at least one acid group and/or esters ofthese acid monomers and/or amides of these acids.

Monomers bearing an acid group that may be used include α,β-ethylenicunsaturated carboxylic acids such as acrylic acid, (meth)acrylic acid,crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid andcrotonic acid are preferably used, and more preferably (meth)acrylicacid.

The acid monomer esters are advantageously chosen from (meth)acrylicacid esters (also known as (meth)acrylates), for instance alkyl(meth)acrylates, in particular of a C₁-C₂₀ and preferably C₁-C₈ alkyl,aryl (meth)acrylates, in particular of a C₆-C₁₀ aryl, and hydroxyalkyl(meth)acrylates, in particular of a C₂-C₆ hydroxyalkyl. Alkyl(meth)acrylates that may be mentioned include methyl, ethyl, butyl,isobutyl, 2-ethylhexyl and lauryl (meth)acrylate. Hydroxyalkyl(meth)acrylates that may be mentioned include hydroxyethyl(meth)acrylate and 2-hydroxypropyl (meth)acrylate. Aryl (meth)acrylatesthat may be mentioned include benzyl or phenyl acrylate.

The (meth)acrylic acid esters that are particularly preferred are thealkyl (meth)acrylates.

Free-radical polymers that are preferably used include copolymers of(meth)acrylic acid and of alkyl (meth)acrylate, especially of a C₁-C₄alkyl. Methyl acrylates optionally copolymerized with acrylic acid maymore preferentially be used.

Amides of the acid monomers that may be mentioned include(meth)acrylamides, especially N-alkyl(meth)-acrylamides, in particularof a C₂-C₁₂ alkyl, such as N-ethylacrylamide, N-t-butylacrylamide andN-octylacrylamide; N-di(C₁-C₄)alkyl(meth)acrylamides.

The acrylic polymers may also result from the polymerization ofethylenically unsaturated monomers containing at least one amine group,in free form or in partially or totally neutralized form, oralternatively in partially or totally quaternized form. Such monomersmay be, for example, dimethylaminoethyl (meth)acrylate,dimethylaminoethyl(meth)acrylamide, vinylamine, vinylpyridine ordiallyldimethylammonium chloride.

The vinyl polymers may also result from the homopolymerization orcopolymerization of at least one monomer chosen from vinyl esters andstyrene monomers. In particular, these monomers may be polymerized withacid monomers and/or esters thereof and/or amides thereof, such as thosementioned previously. Examples of vinyl esters that may be mentionedinclude vinyl acetate, vinyl propionate, vinyl neodecanoate, vinylpivalate, vinyl benzoate and vinyl t-butylbenzoate. Styrene monomersthat may be mentioned include styrene and α-methylstyrene.

The list of monomers given is not limiting, and it is possible to useany monomer known to those skilled in the art included in the categoriesof acrylic and vinyl monomers (including monomers modified with asilicone chain).

As other vinyl monomers that may be used, mention may also be made of:

-   -   N-vinylpyrrolidone, vinylcaprolactam,        vinyl-N—(C₁-C₆)alkylpyrroles, vinyloxazoles, vinylthiazoles,        vinylpyrimidines and vinylimidazoles,    -   olefins such as ethylene, propylene, butylene, isoprene or        butadiene.

The vinyl polymer may be crosslinked with one or more difunctionalmonomers especially comprising at least two ethylenic unsaturations,such as ethylene glycol di(meth)acrylate or diallyl phthalate.

The polymer(s) in dispersion in the organic liquid phase may represent,as solids, from 5% to 40%, preferably from 5% to 35% and better stillfrom 8% to 30% of the weight of the composition.

It is preferably chosen to use a dispersion of film-forming polymerparticles, the particles being dispersed in a volatile oil.

According to one embodiment, the composition contains a stabilizer thatis solid at room temperature. The polymer particles are preferablysurface-stabilized by means of a stabilizer that may be a block polymer,a grafted polymer and/or a random polymer, alone or as a mixture. Thestabilization may take place by any known means, and in particular bydirect addition of the block polymer, grafted polymer and/or randompolymer during the polymerization.

The stabilizer is preferably also present in the mixture beforepolymerization. However, it is also possible to add it continuously,especially when the monomers are also added continuously.

2-30% by weight and preferably 5-20% by weight of stabilizer may be usedrelative to the initial monomer mixture.

Among the grafted polymers that may be mentioned are silicone polymersgrafted with a hydrocarbon-based chain; hydrocarbon-based polymersgrafted with a silicone chain.

Thus, grafted-block or block copolymers comprising at least one block ofpolyorganosiloxane type and at least one block of a free-radicalpolymer, for instance grafted copolymers of acrylic/silicone type, maythus be used, which may be used especially when the non-aqueous mediumis silicone-based.

It is also possible to use grafted-block or block copolymers comprisingat least one block of polyorganosiloxane type and at least one block ofa polyether. The polyorganosiloxane block may especially be apolydimethylsiloxane or a poly(C₂-C₁₈)alkylmethyl-siloxane; thepolyether block may be a poly(C₂-C₁₀-alkylene, in particularpolyoxyethylene and/or polyoxy-propylene. In particular, dimethiconecopolyols or (C₂-C₁₈)alkyldimethicone copolyols such as those sold underthe name Dow Corning 3225C by the company Dow Corning, and laurylmethicones such as those sold under the name Dow Corning Q2-5200 by thecompany Dow Corning, may be used.

Grafted-block or block copolymers that may also be mentioned includethose comprising at least one block resulting from the polymerization ofat least one ethylenic monomer containing one or more optionallyconjugated ethylenic bonds, for instance ethylene or dienes such asbutadiene and isoprene, and of at least one block of a vinyl polymer andbetter still a styrene polymer. When the ethylenic monomer comprisesseveral optionally conjugated ethylenic bonds, the residual ethylenicunsaturations after the polymerization are generally hydrogenated. Thus,in a known manner, the polymerization of isoprene leads, afterhydrogenation, to the formation of an ethylene-propylene block, and thepolymerization of butadiene leads, after hydrogenation, to the formationof an ethylene-butylene block. Among these polymers that may bementioned are block copolymers, especially of “diblock” or “triblock”type such as polystyrene/polyisoprene (SI), polystyrene/polybutadiene(SB) such as those sold under the name Luvitol HSB by BASF, of the typesuch as polystyrene/copoly(ethylene-propylene) (SEP) such as those soldunder the name Kraton by Shell Chemical Co. or of the type such aspolystyrene/copoly(ethylene-butylene) (SEB). Kraton G1650 (SEBS), KratonG1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X(SEP), Kraton G1702X (SEP), Kraton G1726X (SEW, Kraton D-1101 (SBS),Kraton D-1102 (SBS) and Kraton D-1107 (SIS) may be used in particular.The polymers are generally known as hydrogenated or non-hydrogenateddiene copolymers.

Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-(mixture of triblockand of star polymer), Versagel 5960 from Penreco (triblock+starpolymer); OS129880, OS129881 and OS84383 from Lubrizol(styrene/(meth)acrylate copolymer) may also be used.

As grafted-block or block copolymers comprising at least one blockresulting from the polymerization of at least one ethylenic monomercontaining one or more ethylenic bonds and of at least one block of anacrylic polymer, mention may be made of poly(methyl(meth)acrylate)/polyisobutylene diblock or triblock copolymers orgrafted copolymers containing a poly(methyl(meth)acrylate) skeleton andpolyisobutylene grafts.

As grafted-block or block copolymers comprising at least one blockresulting from the polymerization of at least one ethylenic monomercontaining one or more ethylenic bonds and of at least one block of apolyether such as a C₂-C₁₈ polyalkylene (especially polyethylene and/orpolyoxypropylene), mention may be made of polyoxyethylene/polybutadieneor polyoxyethylene/polyisobutylene diblock or triblock copolymers.

Copolymers based on alkyl acrylates or (meth)acrylates derived fromC₁-C₄ alcohols and on alkyl acrylates or (meth)acrylates derived fromC₈-C₃₀ alcohols may thus be used. Mention may be made in particular ofstearyl (meth)acrylate/methyl (meth)acrylate copolymer.

When the liquid synthesis solvent comprises at least one silicone oil,the stabilizer is preferably chosen from the group consisting ofgrafted-block or block copolymers comprising at least one block ofpolyorganosiloxane type and at least one block of a free-radical polymeror of a polyether or of a polyester, for instance polyoxypropyleneand/or polyoxyethylene blocks.

When the liquid organic phase does not comprise any silicone oil, thestabilizer is preferably chosen from the group formed by:

-   -   (a) grafted-block or block copolymers comprising at least one        block of polyorganosiloxane type and at least one block of a        free-radical polymer or of a polyether or a polyester,    -   (b) copolymers of alkyl acrylates or (meth)acrylates derived        from C₁-C₄ alcohols and of alkyl acrylates or (meth)acrylates        derived from C₈-C₃₀ alcohols,    -   (c) grafted-block or block copolymers comprising at least one        block resulting from the polymerization of at least one        ethylenic monomer containing conjugated ethylenic bonds,

and at least one block of a vinyl or acrylic polymer or of a polyetheror of a polyester, or mixtures thereof.

Diblock polymers are preferably used as stabilizer.

When the polymer has a glass transition temperature that is too high forthe intended application, a plasticizer may be combined therewith. Theplasticizer may be chosen from the plasticizers usually used in thefield of application and especially from compounds liable to be solventsfor the polymer. Coalescers may also be used in order to aid the polymerto form a continuous and homogeneous deposit.

The coalescers or plasticizers that may be used in the invention areespecially those mentioned in document FR-A-2 782 917.

The composition may contain a polymer plasticizer, so as to lower the Tgof the polymer film and to improve the adhesion of the polymer film toits support, in particular to keratin materials. The plasticizerespecially lowers the glass transition temperature of the polymer by atleast 2, 3 or 4° C. and preferably from 5° C. to 20° C. In one preferredembodiment, the plasticizer especially lowers the glass transitiontemperature of the polymer by at least 2, 3 or 4° C. and preferably from5° C. to 20° C., when the plasticizer represents not more than 10% byweight of the polymer.

According to one embodiment, the compound may be chosen from esters ofat least one carboxylic acid comprising 1 to 7 carbon atoms and of apolyol comprising at least four hydroxyl groups.

The polyol according to the invention may be a saccharide or asaccharide-based polyol, such as erythritol, xylitol or sorbitol. Thepolymer may be a monosaccharide or a polysaccharide comprising 1 to 10saccharides, preferably from 1 to 4 and more preferably or 2saccharides. The polyol may be chosen from erythritol, xylitol,sorbitol, glucose and sucrose.

The polyol according to the invention is preferably a disaccharide.Among the disaccharides that may be mentioned are sucrose(α-D-glucopyranosyl-(1-2)-β-D-fructofuranose), lactose(β-D-galactopyranosyl-(1-4)-β-D-glucopyranose) and maltose(α-D-glucopyranosyl-(1-4)-β-D-glucopyranose).

The plasticizer may be formed from a polyol substituted with at leasttwo different monocarboxylic acids, or with at least three differentmonocarboxylic acids. The acid is preferably a monocarboxylic acidchosen in particular from acids comprising 1 to 7 carbon atoms andpreferably 1 to 5 carbon atoms, for example acetic acid, n-propanoicacid, isopropanoic acid, n-butanoic acid, isobutanoic acid,tert-butanoic acid, n-pentanoic acid and benzoic acid.

According to one preferred embodiment, the ester is sucrose diacetatehexakis(2-methylpropanoate).

Synthesis Solvent for the Polymer Particles

The polymer dispersion may be manufactured as described in documentEP-A-749 747.

A mixture comprising the initial monomers and also a free-radicalinitiator is prepared. This mixture is dissolved in a solvent referredto hereinbelow in the present description as the “synthesis solvent”.When the fatty phase is a non-volatile oil, the polymerization may beperformed in an apolar organic solvent (synthesis solvent), followed byadding the non-volatile oil (which should be miscible with the saidsynthesis solvent) and selectively distilling off the synthesis solvent.

A synthesis solvent which is such that the initial monomers and thefree-radical initiator are soluble therein, and the polymer particlesobtained are insoluble therein, so that they precipitate during theirformation, is chosen. In particular, the synthesis solvent may be chosenfrom alkanes such as heptane, isododecane and cyclohexane.

When the fatty phase chosen is a volatile oil, the polymerization may beperformed directly in the said oil, which thus also acts as synthesissolvent. The monomers should also be soluble therein, as should thefree-radical initiator, and the polymer obtained should be insolubletherein.

The monomers are preferably present in the synthesis solvent, beforepolymerization, in a proportion of 5-201 by weight of the reactionmixture. The total amount of monomers may be present in the solventbefore the start of the reaction, or part of the monomers may be addedgradually as the polymerization reaction proceeds.

The free-radical initiator may especially be azobisisobutyronitrile ortert-butylperoxy-2-ethyl hexanoate.

The volatile phase of the composition may be formed from or comprise thesynthesis solvent for the dispersed polymer particles.

Additional Polymer:

The compositions according to the invention may contain, besides thefilm-forming polymers described previously, an additional film-formingor non-film-forming polymer.

The composition may comprise an aqueous phase and the additional polymermay be present in this aqueous phase. In this case, the polymer willpreferably be a polymer in dispersion or an amphiphilic or associativepolymer.

The term “polymer in dispersion” means the water-insoluble polymerspresent in the form of particles of variable size. The polymer may ormay not be crosslinked. The size of the polymer particles is typicallybetween 25 and 500 nanometres and preferably between 50 and 200nanometres. The following polymers in aqueous dispersion may be used:Ultrasol 2075 from Ganz Chemical, Daitosol 5000 AD from Daito Kasei,Avalure UR 450 from Noveon, DynamX from National Starch, Syntran 5760from Interpolymer, Acusol OP 301 and from Rohm & Haas, and Neocryl A1090 from Avecia.

The acrylic dispersions sold under the names Neocryl XK-90®, NeocrylA-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and NeocrylA-523® by the company Avecia-Neoresins, Dow Latex 432® by the companyDow Chemical, Daitosol 5000 AD® or Daitosol 5000 SJ® by the companyDaito Kasey Kogyo; Syntran 5760® by the company Interpolymer, Soltex OPTby the company Rohm & Haas, aqueous dispersions of acrylic orstyrene/acrylic polymers sold under the brand name Joncryl® by thecompany Johnson Polymer, or the aqueous dispersions of polyurethane soldunder the names Neorez R-981® and Neorez R-974® by the companyAvecia-Neoresins, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®,Avalure UR-450®, Sancure 875®, Sancure 861®, Sancure 878® and Sancure2060® by the company Goodrich, Impranil 85® by the company Bayer andAquamere H-1511® by the company Hydromer; the sulfopolyesters sold underthe brand name Eastman AQ® by the company Eastman Chemical Products, andvinyl dispersions, for instance Mexomer PAM® from the company Chimex,and mixtures thereof, are other examples of aqueous dispersions ofwater-dispersible film-forming polymer particles.

The term “amphiphilic or associative polymers” means polymers comprisingone or more hydrophilic parts that make them partially water-soluble andone or more hydrophobic parts via which the polymers associate orinteract. The following associative polymers may be used: Nuvis FX 1100from Elementis, Aculyn 22, Aculyn 44 and Aculyn 46 from Rohm & Haas,Viscophobe DB 1000 from Amerchol. Diblock copolymers formed from ahydrophilic block (polyacrylate or polyethylene glycol) and from ahydrophobic block (polystyrene or polysiloxane) may also be used.

Polymers that are soluble in an aqueous phase containing monodisperseparticles may be avoided, since they may cause aggregation of themonodisperse particles. The film-forming polymer may thus be insolublein such an aqueous phase.

The composition may comprise an oily phase and the film-forming polymermay be present in this oily phase. The polymer may then be in dispersionor in solution. Microgels (for example KSG) may be used, as may polymersof the type PS-PA or styrene-based copolymers (Kraton, Regalite).

As examples of lipodispersible non-aqueous film-forming polymerdispersions in the form of non-aqueous dispersions of polymer particlesin one or more silicone and/or hydrocarbon-based oils, which may besurface-stabilized with at least one stabilizer, especially a block,grafted or random polymer, mention may be made of acrylic dispersions inisododecane, for instance Mexomer PAP from the company Chimex, anddispersions of particles of a grafted ethylenic polymer, preferably anacrylic polymer, in a liquid fatty phase, the ethylenic polymeradvantageously being dispersed in the absence of additional stabilizerat the surface of the particles as described especially in document WO04/055 081.

Among the additional film-forming polymers that may be used in thecomposition of the present invention, mention may be made of syntheticpolymers, of free-radical type or of polycondensate type, and polymersof natural origin, and mixtures thereof.

The expression “free-radical film-forming polymer” means a polymerobtained by polymerization of unsaturated and especially ethylenicallyunsaturated monomers, each monomer being capable of homopolymerizing(unlike polycondensates).

The film-forming polymers of free-radical type may be, in particular,vinyl polymers or copolymers, in particular acrylic polymers.

The vinyl film-forming polymers may result from the polymerization ofethylenically unsaturated monomers containing at least one acidic groupand/or esters of these acidic monomers and/or amides of these acidicmonomers.

Monomers bearing an acidic group which may be used are α,β-ethylenicunsaturated carboxylic acids such as acrylic acid, methacrylic acid,crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid andcrotonic acid are preferably used, and more preferably (meth)acrylicacid.

The esters of acidic monomers are advantageously chosen from(meth)acrylic acid esters (also known as (meth)acrylates), especially(meth)acrylates of an alkyl, in particular of a C₁-C₃₀ and preferablyC₁-C₂₀ alkyl, (meth)acrylates of an aryl, in particular of a C₆-C₁₀aryl, and (meth)acrylates of a hydroxyalkyl, in particular of a C₂-C₆hydroxyalkyl.

Among the alkyl (meth)acrylates that may be mentioned are methylmethacrylate, ethyl methacrylate, butyl methacrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate andcyclohexyl methacrylate.

Among the hydroxyalkyl (meth)acrylates that may be mentioned arehydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethylmethacrylate and 2-hydroxypropyl methacrylate.

Among the aryl (meth)acrylates that may be mentioned are benzyl acrylateand phenyl acrylate.

The (meth)acrylic acid esters that are particularly preferred are thealkyl (meth)acrylates.

According to the present invention, the alkyl group of the esters may beeither fluorinated or perfluorinated, i.e. some or all of the hydrogenatoms of the alkyl group are substituted with fluorine atoms.

Examples of amides of the acid monomers that may be mentioned are(meth)acrylamides, and especially N-alkyl(meth)acrylamides, inparticular of a C₂-C₁₂ alkyl. Among the N-alkyl(meth)acrylamides thatmay be mentioned are N-ethylacrylamide, N-t-butylacrylamide,N-t-octylacrylamide and N-undecylacrylamide.

The vinyl film-forming polymers may also result from thehomopolymerization or copolymerization of monomers chosen from vinylesters and styrene monomers. In particular, these monomers may bepolymerized with acid monomers and/or esters thereof and/or amidesthereof, such as those mentioned above.

Examples of vinyl esters that may be mentioned are vinyl acetate, vinylneodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.

Styrene monomers that may be mentioned are styrene and α-methylstyrene.

Among the film-forming polycondensates that may be mentioned arepolyurethanes, polyesters, polyester-amides, polyamides, epoxyesterresins and polyureas.

The polyurethanes may be chosen from anionic, cationic, nonionic andamphoteric polyurethanes, polyurethane-acrylics,polyurethane-polyvinyl-pyrrolidones, polyester-polyurethanes,polyether-polyurethanes, polyureas and polyurea-polyurethanes, andmixtures thereof.

The polyesters may be obtained, in a known manner, by polycondensationof dicarboxylic acids with polyols, in particular diols.

The dicarboxylic acid may be aliphatic, alicyclic or aromatic. Examplesof such acids that may be mentioned are: oxalic acid, malonic acid,dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacicacid, fumaric acid, maleic acid, itaconic acid, phthalic acid,dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid,2,5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid,2,5-naphthalene-dicarboxylic acid or 2,6-naphthalenedicarboxylic acid.These dicarboxylic acid monomers may be used alone or as a combinationof at least two dicarboxylic acid monomers. Among these monomers, theones preferentially chosen are phthalic acid, isophthalic acid andterephthalic acid.

The diol may be chosen from aliphatic, alicyclic and aromatic diols. Thediol used is preferably chosen from: ethylene glycol, diethylene glycol,triethylene glycol, 1,3-propanediol, cyclohexanedimethanol and4-butanediol. Other polyols that may be used are glycerol,pentaerythritol, sorbitol and trimethylol-propane.

The polyesteramides may be obtained in a manner analogous to that of thepolyesters, by polycondensation of diacids with diamines or aminoalcohols. Diamines that may be used are ethylenediamine,hexamethylenediamine and meta- or para-phenylenediamine. An aminoalcohol that may be used is monoethanolamine.

The polyester may also comprise at least one monomer bearing at leastone group —SO₃M, with M representing a hydrogen atom, an ammonium ionNH₄ ⁺ or a metal ion such as, for example, an Na⁺, Li⁺, K⁺, Mg²⁺, Ca²⁺,Cu²⁺, Fe²⁺ or Fe³⁺ ion. A difunctional aromatic monomer comprising sucha group —SO₃M may be used in particular.

The aromatic nucleus of the difunctional aromatic monomer also bearing agroup —SO₃M as described above may be chosen, for example, from benzene,naphthalene, anthracene, biphenyl, oxybiphenyl, sulfonylbiphenyl andmethylenebiphenyl nuclei. As examples of difunctional aromatic monomersalso bearing a group —SO₃M, mention may be made of: sulfoisophthalicacid, sulfoterephthalic acid, sulfophthalic acid,4-sulfonaphthalene-2,7-dicarboxylic acid.

According to one example of a composition according to the invention,the film-forming polymer may be a polymer dissolved in a liquid fattyphase comprising organic solvents or oils (the film-forming polymer isthus said to be a liposoluble polymer). The liquid fatty phasepreferably comprises a volatile oil, optionally mixed with anon-volatile oil.

Examples of liposoluble polymers that may be mentioned are copolymers ofvinyl ester (the vinyl group being directly linked to the oxygen atom ofthe ester group and the vinyl ester containing a saturated, linear orbranched hydrocarbon-based radical of 1 to 19 carbon atoms, linked tothe carbonyl of the ester group) and of at least one other monomer whichmay be a vinyl ester (other than the vinyl ester already present), anα-olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether(in which the alkyl group comprises from 2 to 18 carbon atoms) or anallylic or methallylic ester (containing a saturated, linear or branchedhydrocarbon-based radical of 1 to 19 carbon atoms, linked to thecarbonyl of the ester group).

These copolymers may be crosslinked with the aid of crosslinking agents,which may be either of the vinyl type or of the allylic or methallylictype, such as tetraallyloxyethane, divinylbenzene, divinyloctane-dioate, divinyl dodecanedioate and divinyl octadecane-dioate.

Examples of these copolymers that may be mentioned are the followingcopolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate,vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinylacetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinylpropionate/vinyl laurate, vinyl stearate/1-octadecene, vinylacetate/1-dodecene, vinyl stearate/ethyl vinyl ether, vinylpropionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl2,2-dimethyloctanoate/vinyl laurate, allyl 2,2-dimethylpentanoate/vinyllaurate, vinyl dimethylpropionate/vinyl stearate, allyldimethylpropionate/vinyl stearate, vinyl propionate/vinyl stearate,crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate/vinyllaurate, crosslinked with 0.2% divinylbenzene, vinyl acetate/octadecylvinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinylacetate/allyl stearate, crosslinked with 0.2% divinyl-benzene, vinylacetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and allylpropionate/allyl stearate, crosslinked with 0.26 divinylbenzene.

Examples of liposoluble film-forming polymers that may be mentionedinclude copolymers of a vinyl ester and of at least one other monomerthat may be a vinyl ester, especially vinyl neodecanoate, vinyl benzoateand vinyl t-butylbenzoate, an α-olefin, an alkyl vinyl ether or anallylic or methallylic ester.

Examples of liposoluble film-forming polymers that may also be mentionedare liposoluble copolymers, and in particular those resulting from thecopolymerization of vinyl esters containing from 9 to 22 carbon atoms orof alkyl acrylates or methacrylates, and alkyl radicals containing from10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen from copolymers of polyvinylstearate, polyvinyl stearate crosslinked with the aid of divinylbenzene,of diallyl ether or of diallyl phthalate, polystearyl (meth)acrylate,polyvinyl laurate and polylauryl (meth)acrylate, it being possible forthese poly(meth)acrylates to be crosslinked with the aid of ethyleneglycol dimethacrylate or tetraethylene glycol dimethacrylate.

The liposoluble copolymers defined above are known and are described inparticular in patent application FR-A-2 232 303; they may have aweight-average molecular weight ranging from 2000 to 500 000 andpreferably from 4000 to 200 000.

As liposoluble film-forming polymers that may be used in the invention,mention may also be made of polyalkylenes and in particular copolymersof C₂-C₂₀ alkenes, such as polybutene, alkylcelluloses with a linear orbranched, saturated or unsaturated C₁-C₈ alkyl radical, for instanceethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP)and in particular copolymers of vinylpyrrolidone and of C₂ to C₄₀ andbetter still C₃ to C₂₀ alkene. As examples of VP copolymers which may beused in the invention, mention may be made of the copolymers of VP/vinylacetate, VP/ethyl methacrylate, butylated polyvinyl-pyrrolidone (PVP),VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene,VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate.

Mention may also be made of silicone resins, which are generally solubleor swellable in silicone oils, which are crosslinked polyorganosiloxanepolymers. The nomenclature of silicone resins is known under the name“MDTQ”, the resin being described as a function of the various siloxanemonomer units it comprises, each of the letters “MDTQ” characterizing atype of unit.

Examples of commercially available polymethyl-silsesquioxane resins thatmay be mentioned include those sold by the company Wacker under thereference Resin MK, such as Belsil PMS MK, or by the company Shin-Etsuunder the reference KR-220L.

Examples of commercially available polypropyl-silsesquioxane resins thatmay be mentioned include those sold under the reference DC670 by thecompany Dow Corning.

Siloxysilicate resins that may be mentioned include trimethylsiloxysilicate (TMS) resins such as those sold under the reference SR1000 by the company General Electric or under the reference TMS 803 bythe company Wacker. Mention may also be made of the trimethylsiloxysilicate resins sold in a solvent such as cyclomethicone, soldunder the name KF-7312J by the company Shin-Etsu, and DC 749 and DC 593by the company Dow Corning.

In the case of skin makeup or care compositions, the combination of aresin according to the invention with a trimethyl siloxysilicate resinor a polypropylsilsesquioxane resin makes it possible to improve thedurability of the transfer resistance.

Mention may also be made of silicone resin copolymers such as thosementioned above with polydimethylsiloxanes, for instance thepressure-sensitive adhesive copolymers sold by the company Dow Corningunder the reference Bio-PSA and described in document U.S. Pat. No.5,162,410, or the silicone copolymers derived from the reaction of asilicone resin, such as those described above, and of adiorganosiloxane, as described in document WO 2004/073 626.

The film-forming polymer may be chosen from block or random polymersand/or copolymers especially comprising polyurethanes, polyacrylics,silicones, fluoro polymers, butyl rubbers, ethylene copolymers, naturalgums and polyvinyl alcohols, and mixtures thereof. The monomers of theblock or random copolymers comprising at least one combination ofmonomers whose resulting polymer has a glass transition temperature ofless than room temperature (25° C.) may be chosen especially frombutadiene, ethylene, propylene, acrylic, methacrylic, isoprene,isobutene and a silicone, and mixtures thereof.

The film-forming polymer may also be present in the first and/or secondcomposition in the form of particles dispersed in an aqueous phase or ina non-aqueous solvent phase, which is generally known as a latex orpseudolatex. The techniques for preparing these dispersions are wellknown to those skilled in the art.

The composition according to the invention may comprise a plasticizerthat promotes the formation of a film with the film-forming polymer.Such a plasticizer may be chosen from any compound known to thoseskilled in the art as being capable of satisfying the desired function.

As other examples of film-forming systems that may be used in thecompositions according to the invention, mention may be made of systemsin which the film is formed in situ at the time of application of thecomposition or of a mixture of compositions containing two siliconecompounds that react together when they are placed in contact. Suchsystems are described especially in patent application WO 2007/071 706,the content of which is incorporated herein by reference. Systems ofthis type are also described in patent applications US 2007/142 575 andUS 2007/142 599, the content of which is also incorporated herein byreference.

Other Polymers:

The compositions according to the invention may contain an elastomer,especially a polyglycerolated silicone elastomer. By way of example, useis made of an elastomeric crosslinked organopolysiloxane that may beobtained by a crosslinking addition reaction of a diorganopolysiloxanecontaining at least one hydrogen bonded to silicon and ofpolyglycerolated compounds containing ethylenically unsaturated groups,especially in the presence of a platinum catalyst.

Polyglycerolated silicone elastomers that may be used include those soldunder the names KSG-710, KSG-810, KSG-820, KSG-830 and KSG-840 by thecompany Shin-Etsu.

The compositions according to the invention may also comprise anadditional emulsifying silicone elastomer.

By way of example, use may be made of polyoxyalkylenated elastomers asdescribed especially in U.S. Pat. No. 5,236,986, U.S. Pat. No.5,412,004, U.S. Pat. No. 5,837,793 and U.S. Pat. No. 5,811,487, thecontent of which is incorporated by reference.

Polyoxyalkylenated silicone elastomers that may be used include thosesold under the names KSG-21, KSG-20, KSG-30, KSG-31, KSG-32, KSG-33,KSG-210, KSG-310, KSG-320, KSG-330, KSG-340 and X-226146 by the companyShin-Etsu, and DC9010 and DC9011 by the company Dow Corning.

When they are in combination with the resins according to the invention,these particular elastomers may make it possible to improve thetransfer-resistance and comfort (suppleness) properties of thecompositions comprising them.

The compositions according to the invention may also comprise anon-emulsifying elastomer.

Non-emulsifying elastomers are especially described in patentapplications JP-A-61-194 009, EP-A-242 219, EP-A-285 886 and EP-A-765656, the content of which is incorporated by reference.

Spherical non-emulsifying elastomers that may be used include those soldunder the names DC9040, DC9041, DC9509, DC9505 and DC9506 by the companyDow Corning.

The spherical non-emulsifying silicone elastomer may also be in the formof an elastomeric crosslinked organopolysiloxane powder coated withsilicone resin, especially with silsesquioxane resin, as described, forexample, in U.S. Pat. No. 5,538,793, the content of which isincorporated by reference. Such elastomers are sold under the namesKSP-100, KSP-101, KSP-102, KSP-103, KSP-104 and KSP-105 by the companyShin-Etsu.

Other elastomeric crosslinked organopolysiloxanes in the form ofspherical powders may be powders of a hybrid silicone functionalizedwith fluoroalkyl groups, sold especially under the name KSP-200 by thecompany Shin-Etsu; powders of a hybrid silicone functionalized withphenyl groups, sold especially under the name KSP-300 by the companyShin-Etsu.

Silicone elastomers bearing a group MQ, such as those sold by thecompany Wacker under the names Belsil RG100, Belsil RPG33 and,preferentially, RG80, may also be used in the compositions according tothe invention. These particular elastomers, when they are in combinationwith the resins according to the invention, may make it possible toimprove the transfer-resistance properties of the compositionscomprising them.

The Oils:

The composition according to the invention comprises at least one liquidfatty phase comprising at least one oil.

The oil may be chosen from hydrocarbon-based oils, silicone oils andfluoro oils.

The oil may be chosen from volatile oils and non-volatile oils, andmixtures thereof.

The term “hydrocarbon-based oil” means an oil formed essentially from,or even consisting of, carbon and hydrogen atoms, and possibly oxygenand nitrogen atoms, and containing no silicon or fluorine atoms; it maycontain ester, ether, amine or amide groups.

The term “silicone oil” means an oil containing at least one siliconatom, and especially containing Si—O groups.

The term “fluoro oil” means an oil containing at least one fluorineatom.

The composition according to the invention may comprise at least onevolatile oil.

The term “volatile oil” means an oil (or non-aqueous medium) capable ofevaporating on contact with the skin in less than one hour, at roomtemperature and atmospheric pressure. The volatile oil is a volatilecosmetic oil, which is liquid at room temperature, especially having anon-zero vapour pressure, at room temperature and atmospheric pressure,in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa(10⁻³ to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10mmHg).

In addition, the volatile oil generally has a boiling point, measured atatmospheric pressure, ranging from 150° C. to 260° C. and preferablyranging from 170° C. to 250° C.

The composition according to the invention may comprise a volatilehydrocarbon-based oil chosen especially from hydrocarbon-based oils witha flash point ranging from 40° C. to 102° C., preferably ranging from40° C. to 55° C. and preferentially ranging from 40° C. to 50° C.

Volatile hydrocarbon-based oils that may be mentioned include volatilehydrocarbon-based oils containing from 8 to 16 carbon atoms and mixturesthereof, and especially branched C₈-C₁₆ alkanes, for instance C₈-C₁₆isoalkanes (also known as isoparaffins), isododecane, isodecane,isohexadecane and, for example, the oils sold under the trade nameIsopar or Permethyl, branched C₈-C₁₆ esters, for instance isohexylneopentanoate, and mixtures thereof. Preferably, the volatilehydrocarbon-based oil is chosen from volatile hydrocarbon-based oilscontaining from 8 to 16 carbon atoms, and mixtures thereof, inparticular from isododecane, isodecane and isohexadecane, and isespecially isododecane.

For skin makeup products, especially foundations and lipsticks, linearhydrocarbon-based volatile oils containing from 8 to 16 carbon atomswill advantageously be used.

Volatile silicone oils that may be mentioned include linear or cyclicsilicones containing from 2 to 7 silicon atoms, these siliconesoptionally comprising alkyl or alkoxy groups containing from 1 to 10carbon atoms. As volatile silicone oils that may be used in theinvention, mention may be made especially ofoctamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, heptamethyl-hexyltrisiloxane,heptamethyloctyltrisiloxane, octamethyltrisiloxane anddecamethyltetrasiloxane, and mixtures thereof.

The volatile oil may be present in the composition according to theinvention in a content ranging from 0.1% to 90% by weight, preferablyranging from 1% to 70% by weight and preferentially ranging from 5% to50% by weight, relative to the total weight of the composition.

The composition according to the invention may comprise at least onenon-volatile oil.

Non-volatile hydrocarbon-based oils that may be used include liquidparaffin (or petroleum jelly), squalane, hydrogenated polyisobutylene(Parleam oil), perhydrosqualene, mink oil, turtle oil, soybean oil,sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, sesame seedoil, corn oil, arara oil, rapeseed oil, sunflower oil, cottonseed oil,apricot oil, castor oil, avocado oil, jojoba oil, olive oil or cerealgerm oil; linoleic acid, oleic acid, lauric acid or stearic acid esters;fatty esters, especially of C₁₂-C₃₆, such as isopropyl myristate,isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate,isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate,2-octyldecyl palmitate, 2-octyldodecyl myristate or lactate,bis(2-ethylhexyl) succinate, diisostearyl malate, and glyceryl ordiglyceryl triisostearate; behenic acid, oleic acid, linoleic acid,linolenic acid or isostearic acid; higher fatty alcohols, especially ofC₁₆-C₂₂, such as cetanol, oleyl alcohol, linoleyl alcohol, linolenylalcohol, isostearyl alcohol or octyldodecanol; and mixtures thereof.

The non-volatile oil may be present in a content ranging from 0.1% to70% by weight, preferably ranging from 0.5% to 60% by weight andpreferentially ranging from 1% to 50% by weight relative to the totalweight of the non-volatile liquid fatty phase.

For skin makeup products, especially foundations and lipsticks, volatileor non-volatile linear silicone oils will advantageously be used. Thecombination of a resin according to the invention and of a linearsilicone oil may especially improve the transfer resistance.

For skin makeup products, especially lipsticks, phenyl silicone oilswill advantageously be used. The combination of a resin according to theinvention and of a phenyl silicone oil may especially improve the glossand comfort and reduce the tacky sensation.

Structuring Agents:

The composition according to the invention may comprise a structuringagent.

The term “structuring agent” means a compound capable of increasing theviscosity of the composition. The structuring agent makes it possibleespecially to obtain a composition that can have a texture ranging fromfluid to solid textures.

The structuring agent may be present in the composition in a contentranging from 0.05% to 40% by weight, preferably ranging from 0.1% to 30%by weight and preferentially ranging from 0.1% to 25% by weight,relative to the total weight of the composition.

The structuring agent may be chosen especially from thickeners(oily-medium thickeners; aqueous-medium thickeners), organogellingagents, waxes, pasty compounds and gums.

The aqueous-medium thickener may be chosen from:

-   -   hydrophilic clays,    -   hydrophilic fumed silica,    -   water-soluble cellulose-based thickeners,    -   guar gum, xanthan gum, carob gum, scleroglucan gum, gellan gum,        rhamsan gum, karaya gum or carrageenan gum,    -   alginates, maltodextrins, starch and its derivatives, and        hyaluronic acid and its salts,    -   the polyglyceryl (meth)acrylate polymers sold under the names        “Hispagel” or “Lubragel” by the companies Hispano Quimica or        Guardian,    -   polyvinylpyrrolidone,    -   polyvinyl alcohol,    -   crosslinked acrylamide polymers and copolymers, such as those        sold under the names PAS 5161 or Bozepol C by the company        Hoechst, Sepigel 305 by the company SEPPIC by the company Allied        Colloid, or alternatively    -   the crosslinked methacryloyloxyethyltrimethyl-ammonium chloride        homopolymers sold under the name “Salcare SC95” by the company        Allied Colloid,    -   associative polymers and especially associative polyurethanes.

Such thickeners are described especially in patent application EP-A-1400 234, the content of which is incorporated by reference.

The oily-medium thickener may be chosen from:

-   -   carboxylate silicones,    -   saccharide silicones,    -   organophilic clays;    -   hydrophobic fumed silicas;    -   alkyl guar gums (with a C₁-C₆ alkyl group), such as those        described in EP-A-708 114;    -   hydrophobic celluloses,    -   oil-gelling polymers, for instance triblock polymers or star        polymers resulting from the polymerization or copolymerization        of at least one monomer containing an ethylenic group, for        instance the polymers sold under the name Kraton;    -   polymers with a weight-average molecular mass of less than 100        000, comprising a) a polymer skeleton containing        hydrocarbon-based repeating units containing at least one        heteroatom, and optionally b) at least one pendent fatty chain        and/or at least one terminal fatty chain, which are optionally        functionalized, containing from 6 to 120 carbon atoms and being        linked to these hydrocarbon-based units, as described in patent        applications WO-A-02/056847 and WO-A-02/47619, the content of        which is incorporated by reference; in particular, polyamide        resins (especially comprising alkyl groups containing from 12 to        22 carbon atoms) such as those described in U.S. Pat. No.        5,783,657, the content of which is incorporated by reference;    -   the silicone-based polyamide resins as described in patent        application EP-A-1 266 647 and in the French patent application        filed under the number 0 216 039, the content of which is        incorporated by reference.

Such thickeners are especially described in patent application EP-A-1400 234, the content of which is incorporated by reference.

The organogelling agents may be chosen from those described in patentapplication WO-A-03/105 788, the content of which is incorporated byreference.

In particular, it may be advantageous to combine the resins according tothe invention with particular organogelling agents, and especially:

the bis-urea derivatives of general formula (I):

in which:

A is a group of formula:

with R′ being a linear or branched C₁ to C₄ alkyl radical and the *ssymbolizing the points of attachment of the group A to each of the twonitrogen atoms of the rest of the compound of general formula (I), and

-   -   R is a saturated or unsaturated, non-cyclic, mono-branched C₆ to        C₁₆ alkyl radical whose hydrocarbon-based chain is optionally        interrupted with 1 to 3 heteroatoms chosen from O, S and N, or

a salt or isomer thereof, described especially in patent applicationFR-A-2 892 303,

the silicone bis-urea derivatives of general formula (I), or a saltand/or isomer thereof:

in which:

-   -   A is a group of formula (II):

with R₁ being a linear or branched C₁-C₄ alkyl radical, and the *ssymbolizing the points of attachment of the group A to each of the twonitrogen atoms of the rest of the compound of general formula (I), and

-   -   R and R′, which may be identical or different, are chosen from:    -   i) the radicals of formula (III):

in which:

-   -   L is a single bond or a divalent carbon-based radical,        especially a linear, branched and/or cyclic, saturated or        unsaturated hydrocarbon-based radical (alkylene), containing 1        to 18 carbon atoms, and possibly comprising 1 to 4 heteroatoms        chosen from N, O and S;    -   R_(a) is:

a) a carbon-based radical, especially a linear, branched and/or cyclic,saturated or unsaturated hydrocarbon-based radical (alkyl), containing 1to 18 carbon atoms, and possibly comprising 1 to 8 heteroatoms chosenfrom N, O, Si and S; or

b) a silicone radical of formula:

with n being between 0 and 100, especially between 1 and 80, or even 2to 20;

and R₂ to R₆ being, independently of each other, carbon-based radicals,especially linear or branched hydrocarbon-based radicals (alkyl)containing 1 to 12 and especially 1 to 6 carbon atoms, and possiblycomprising 1 to 4 heteroatoms, especially O;

-   -   R_(b) and R_(c) are, independently of each other, chosen from:

a) carbon-based radicals, especially linear, branched and/or cyclic,saturated or unsaturated hydrocarbon-based radicals (alkyl), containing1 to 18 carbon atoms, and possibly comprising 1 to 4 heteroatoms chosenfrom N, O, Si and S;

b) the radicals of formula:

with n being between 0 and 100, especially between 1 and 80, or even 2to 20;

and R′₂ to R′₆ being, independently of each other, carbon-basedradicals, especially linear or branched hydrocarbon-based radicals(alkyl), containing 1 to 12 and especially 1 to 6 carbon atoms, andpossibly comprising 1 to 4 heteroatoms, especially O; and

-   -   ii) linear, branched and/or cyclic, saturated or unsaturated        C₁-C₃₀ alkyl radicals, optionally comprising 1 to 3 heteroatoms        chosen from O, S, F and N;

it being understood that at least one of the radicals R and/or R′ is offormula (III), such as those described in patent application FR-A-2 900819,

the bis-urea derivatives described in patent application FR-A-2 8994476.

Wax(es)

The composition may comprise at least one solid fatty substance chosenfrom waxes, as structuring agent.

The wax under consideration in the context of the present invention isgenerally a lipophilic compound that is solid at room temperature (25°C.), with a solid/liquid reversible change of state, having a meltingpoint of greater than or equal to 30° C., which may be up to 200° C. andin particular up to 120° C.

In particular, the waxes that are suitable for the invention may have amelting point of greater than or equal to 45° C. and in particulargreater than or equal to 55° C.

For the purposes of the invention, the melting point corresponds to thetemperature of the most endothermic peak observed by thermal analysis(DSC) as described in standard ISO 11357-3; 1999. The melting point ofthe wax may be measured using a differential scanning calorimeter (DSC),for example the calorimeter sold under the name MDSC 2920 by the companyTA Instruments.

The measuring protocol is as follows:

A sample of 5 mg of wax placed in a crucible is subjected to a firsttemperature rise ranging from −20° C. to 100° C., at a heating rate of10° C./minute, it is then cooled from 100° C. to −20° C. at a coolingrate of 10° C./minute and is finally subjected to a second temperatureincrease ranging from −20° C. to 100° C. at a heating rate of 5°C./minute. During the second temperature increase, the variation of thedifference in power absorbed by the empty crucible and by the cruciblecontaining the sample of wax is measured as a function of thetemperature. The melting point of the compound is the temperature valuecorresponding to the top of the peak of the curve representing thevariation in the difference in absorbed power as a function of thetemperature.

The waxes that may be used in the compositions according to theinvention are chosen from waxes that are solid at room temperature ofanimal, plant, mineral or synthetic origin, and mixtures thereof.

As illustrations of waxes that are suitable for the invention, mentionmay be made especially of hydrocarbon-based waxes, for instance beeswax,lanolin wax, Chinese insect waxes, rice bran wax, carnauba wax,candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax,Japan wax and sumach wax; montan wax, orange wax and lemon wax,microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, thewaxes obtained by Fischer-Tropsch synthesis and waxy copolymers, andalso esters thereof.

Mention may also be made of waxes obtained by catalytic hydrogenation ofanimal or plant oils containing linear or branched C₈-C₃₂ fatty chains.Among these waxes that may especially be mentioned are isomerized jojobaoil such as the trans-isomerized partially hydrogenated jojoba oilmanufactured or sold by the company Desert Whale under the commercialreference Iso-Jojoba-50®, hydrogenated sunflower oil, hydrogenatedcastor oil, hydrogenated coconut oil, hydrogenated lanolin oil andbis(1,1,1-trimethylol-propane) tetrastearate sold under the name Hest2T-4S® by the company Heterene.

Mention may also be made of silicone waxes (C₃₀₋₄₅ alkyl dimethicone)and fluoro waxes.

The waxes obtained by hydrogenation of castor oil esterified with cetylalcohol, sold under the names Phytowax ricin 16L64® and 22L73® by thecompany Sophim, may also be used. Such waxes are described in patentapplication FR-A-2 792 190.

A wax that may be used is a C₂₀-C₄₀ alkyl (hydroxystearyloxy)stearate(the alkyl group containing from 20 to 40 carbon atoms), alone or as amixture.

Such a wax is especially sold under the names Kester Wax K 82 P®,Hydroxypolyester K 82 P®, Kester Wax K 80 P® and Kester Wax K 82H® bythe company Koster Keunen.

As microwaxes that may be used in the compositions according to theinvention, mention may be made especially of carnauba microwaxes, suchas the product sold under the name MicroCare 350® by the company MicroPowders, synthetic microwaxes, such as the product sold under the nameMicroEase 114S® by the company Micro Powders, microwaxes consisting of amixture of carnauba wax and polyethylene wax, such as the products soldunder the names Micro Care 300® and 310® by the company Micro Powders,microwaxes consisting of a mixture of carnauba wax and of synthetic wax,such as the product sold under the name Micro Care 325® by the companyMicro Powders, polyethylene microwaxes, such as the products sold underthe names Micropoly 200®, 220®, 220L® and 250S® by the company MicroPowders, and polytetrafluoroethylene microwaxes, such as the productssold under the names Microslip 519® and 519 L® by the company MicroPowders.

The composition according to the invention may have a wax contentranging from 0.1% to 50% by weight and better still from 1% to 30% byweight relative to the total weight of the composition.

Pasty Compounds

The composition according to the invention may comprise at least onepasty compound as structuring agent. Pasty fatty substances areconsidered as solid fatty substances for the purposes of the presentinvention.

For the purposes of the present invention, the term “pasty” means alipophilic fatty compound that undergoes a reversible solid/liquidchange of state and that comprises in the solid state an anisotropiccrystal organization, and comprises, at a temperature of 23° C., aliquid fraction and a solid fraction.

In other words, the starting melting point of the pasty compound is lessthan 23° C. The liquid fraction of the pasty compound measured at 23° C.may represent 9% to 97% by weight of the compound. This liquid fractionat 23° C. preferably represents between 15% and 85% and more preferablybetween 40% and 85% by weight.

The liquid fraction by weight of the pasty compound at 23° C. is equalto the ratio of the heat of fusion consumed at 23° C. to the heat offusion of the pasty compound.

The heat of fusion of the pasty compound is the heat consumed by thecompound to change from the solid state to the liquid state. The pastycompound is said to be in the solid state when all of its mass is insolid form. The pasty compound is said to be in the liquid state whenall of its mass is in liquid form.

The heat of fusion of the pasty compound is equal to the area under thecurve of the thermogram obtained using a differential scanningcalorimeter (DSC), such as the calorimeter sold under the name MDSC 2920by the company TA Instrument, with a temperature rise of 5 or 10° C. perminute, according to standard ISO 11357-3:1999. The heat of fusion ofthe pasty compound is the amount of energy required to make the compoundchange from the solid state to the liquid state. It is expressed in J/g.

The heat of fusion consumed at 23° C. is the amount of energy absorbedby the sample to change from the solid state to the state that it has at23° C., constituted of a liquid fraction and a solid fraction.

The liquid fraction of the pasty compound, measured at 32° C.,preferably represents from 30% to 100% by weight of the compound,preferably from 50% to 100% and more preferably from 60% to 100% byweight of the compound. When the liquid fraction of the pasty compoundmeasured at 32° C. is equal to 100%, the temperature of the end of themelting range of the pasty compound is less than or equal to 32° C.

The liquid fraction of the pasty compound measured at 32° C. is equal tothe ratio of the heat of fusion consumed at 32° C. to the heat of fusionof the pasty compound. The heat of fusion consumed at 32° C. iscalculated in the same manner as the heat of fusion consumed at 23° C.

The pasty compound is preferably chosen from synthetic compounds andcompounds of plant origin. A pasty compound may be obtained by synthesisfrom starting materials of plant origin.

The pasty compound may advantageously be chosen from:

-   -   i) lanolin and derivatives thereof,    -   ii) polymer or non-polymer silicone compounds,    -   iii) polymer or non-polymer fluoro compounds,    -   iv) vinyl polymers, especially:    -   v) olefin homopolymers    -   vi) olefin copolymers    -   vii) hydrogenated diene homopolymers and copolymers    -   viii) linear or branched oligomers, which are homopolymers or        copolymers of alkyl (meth)acrylates preferably containing a        C₈-C₃₀ alkyl group    -   ix) oligomers, which are homopolymers and copolymers of vinyl        esters containing C₈-C₃₀ alkyl groups    -   x) oligomers, which are homopolymers and copolymers of vinyl        ethers containing C₈-C₃₀ alkyl groups,    -   xi) liposoluble polyethers resulting from the polyetherification        between one or more C₂-C₁₀₀ and preferably C₂-C₅₀ diols,    -   xii) esters,    -   xiii) and mixtures thereof.

Among the esters that are especially preferred are:

-   -   xiv) esters of a glycerol oligomer, especially diglycerol        esters, in particular condensates of adipic acid and of        glycerol, for which some of the hydroxyl groups of the glycerols        have reacted with a mixture of fatty acids such as stearic acid,        capric acid, stearic acid and isostearic acid, and        12-hydroxystearic acid, especially such as the product sold        under the brand name Softisan 649 by the company Sasol,    -   xv) arachidyl propionate sold under the brand name Waxenol 801        by Alzo,    -   xvi) phytosterol esters,    -   xvii) fatty acid triglycerides and derivatives thereof,    -   xviii) pentaerythritol esters,    -   xix) non-crosslinked polyesters resulting from polycondensation        between a linear or branched C₄-C₅₀ dicarboxylic acid or        polycarboxylic acid and a C₂-C₅₀ diol or polyol,    -   xx) aliphatic esters of an ester resulting from the        esterification of an aliphatic hydroxycarboxylic acid with an        aliphatic carboxylic acid,    -   xxi) polyesters resulting from the esterification, with a        polycarboxylic acid, of an ester of an aliphatic        hydroxycarboxylic acid, the said ester comprising at least two        hydroxyl groups, such as the products Risocast DA-H® and        Risocast DA-L®,    -   xxii) esters of a diol dimer and of a diacid dimer, where        appropriate esterified on their free alcohol or acid function(s)        with acid or alcohol radicals, such as Plandool-G,    -   xxiii) and mixtures thereof.

Among the pasty compounds of plant origin, a mixture of soybean sterolsand of oxyethylenated (5 EO) oxypropylenated (5 PO) pentaerythritol,sold under the reference Lanolide by the company Vevy, will preferablybe chosen.

Preferably, the composition comprises a total content of pasty fattysubstances ranging from 0.5% to 50% by weight, preferably from 1% to 40%by weight and better still from 5% to 30% by weight relative to theweight of the composition.

The gums are generally polydimethylsiloxanes (PDMS) of high molecularweight or cellulose gums or polysaccharides.

Surfactants

The composition according to the invention may comprise at least onesurfactant.

The surfactant may be lipophilic and/or hydrophilic, used alone or incombination.

The surfactant may be chosen from nonionic, anionic, cationic andamphoteric surfactants.

The nonionic surfactant may be chosen from:

-   -   a C₈-C₂₂ alkyl dimethicone copolyol, i.e. an oxypropylenated        and/or oxyethylenated polymethyl (C₈-C₂₂)alkyl dimethyl methyl        siloxane.

The C₈-C₂₂ alkyl dimethicone copolyol is advantageously a compound offormula (I) below:

in which:

-   -   PE represents (—C₂H₄O)_(x)— (C₃H₆O)_(y)—R, R being chosen from a        hydrogen atom and an alkyl radical of 1 to 4 carbon atoms, x        ranging from 0 to 100 and y ranging from 0 to 80, x and y not        simultaneously being 0    -   m ranging from 1 to 40    -   n ranging from 10 to 200    -   o ranging from 1 to 100    -   p ranging from 7 to 21    -   q ranging from 0 to 4

and preferably:

R═H

m=1 to 10

n=10 to 100

o=1 to 30

p=15

q=3.

A C₈-C₂₂ alkyl dimethicone copolyol that may be mentioned is cetyldimethicone copolyol, for instance the product sold under the name AbilEM-90 by the company Goldschmidt.

-   -   a dimethicone copolyol, i.e. an oxypropylenated and/or        oxyethylenated polydimethyl methyl siloxane. It contains no        alkyl groups with a chain length of more than 8 carbon atoms,        especially C₈-C₂₂.

Dimethicone copolyols that may be used include those corresponding toformula (II) below:

in which:

R₁, R₂ and R₃, independently of each other, represent a C₁-C₆ alkylradical or a radical —(CH₂)_(X)—(OCH₂CH₂)_(y)—(OCH₂CH₂CH₂)_(z)—OR₄, atleast one radical R₁, R₂ or R₃ not being an alkyl radical; R₄ being ahydrogen, a C₁-C₂ alkyl radical or a C₂-C₄ acyl radical;

A is an integer ranging from 0 to 200;

B is an integer ranging from 0 to 50; on condition that A and B are notsimultaneously equal to zero;

x is an integer ranging from 1 to 6;

y is an integer ranging from 1 to 30;

z is an integer ranging from 0 to 5.

According to one preferred embodiment of the invention, in the compoundof formula (II), R₁═R₃=methyl radical, x is an integer ranging from 2 to6 and y is an integer ranging from 4 to 30. R₄ is in particular ahydrogen.

Examples of compounds of formula (II) that may be mentioned include thecompounds of formula (III):

in which A is an integer ranging from 20 to 105, B is an integer rangingfrom 2 to 10 and y is an integer ranging from 10 to 20.

Examples of silicone compounds of formula (II) that may also bementioned include the compounds of formula (IV):

HO—(CH₂CH₂O)_(y)—(CH₂)₃-[(CH₃)₂SiO]_(A′)-[(CH₃)₂Si]-(CH₂)₃—(OCH₂CH₂)_(y)—OH  (Iv)

in which A′ and y are integers ranging from 10 to 20.

Dimethicone copolyols that may be used include those sold under thenames DC 5329, DC 7439-146, DC 2-5695 and Q4-3667 by the company DowCorning; KF-6013, KF-6015, KF-6016 and KF-6017 by the company Shin-Etsu.

The compounds DC 5329, DC 7439-146 and DC2-5695 are compounds of formula(III) in which, respectively, A is 22, B is 2 and y is 12; A is 103, Bis 10 and y is 12; A is 27, B is 3 and y is 12.

Nonionic surfactants that may also be mentioned include fatty acidesters of polyols, for instance sorbitol or glyceryl mono-, di-, tri- orsesqui-oleates or stearates, glyceryl or polyethylene glycol laurates;fatty acid esters of polyethylene glycol (polyethylene glycolmonostearate or monolaurate); polyoxyethylenated fatty acid esters(stearate or oleate) of sorbitol; polyoxyethylenated alkyl (lauryl,cetyl, stearyl or octyl)ethers.

Anionic surfactants that may be mentioned include carboxylates (sodium2-(2-hydroxyalkyloxy)acetate)), amino acid derivatives(N-acylglutamates, N-acylglycinates or acylsarcosinates), alkylsulfates, alkyl ether sulfates and oxyethylenated derivatives thereof,sulfonates, isethionates and N-acylisethionates, taurates and N-acylN-methyltaurates, sulfosuccinates, alkylsulfoacetates, phosphates andalkyl phosphates, polypeptides, anionic derivatives of alkylpolyglycoside (acyl-D-galactoside uronate), and fatty acid soaps, andmixtures thereof.

Amphoteric and zwitterionic surfactants that may be used includebetaines, N-alkylamidobetaines and derivatives thereof, glycinederivatives, sultaines, alkyl polyaminocarboxylates andalkylamphoacetates, and mixtures thereof.

Such surfactants are described especially in patent applicationWO-A-02/056 854, the content of which is incorporated by reference.

The surfactant may be present in the composition according to theinvention in a content ranging from 0.1% to 10% by weight, preferablyranging from 0.5% to 8% by weight and preferentially ranging from 0.5%to 7% by weight, relative to the total weight of the composition.

Dyestuffs:

The composition according to the invention may comprise at least onedyestuff.

The dyestuff may be chosen from pulverulent dyestuffs (especiallypigments and nacres) and water-soluble dyestuffs.

The term “pigments” should be understood as meaning white or coloured,mineral or organic particles of any form, which are insoluble in thephysiological medium, and which are intended to colour the composition.

The term “nacres” should be understood as meaning iridescent particlesof any form, produced especially by certain molluscs in their shell, orelse synthesized.

The pigments may be white or coloured, and mineral and/or organic. Amongthe mineral pigments that may be mentioned are titanium dioxide,optionally surface-treated, zirconium oxide or cerium oxide, and alsozinc oxide, iron oxide (black, yellow or red) or chromium oxide,manganese violet, ultramarine blue, chromium hydrate and ferric blue,and metal powders, for instance aluminium powder or copper powder.

Among the organic pigments that may be mentioned are carbon black,pigments of D & C type, and lakes based on cochineal carmine or onbarium, strontium, calcium or aluminium.

Mention may also be made of pigments with an effect, such as particlescomprising a natural or synthetic, organic or mineral substrate, forexample glass, acrylic resins, polyester, polyurethane, polyethyleneterephthalate, ceramics or aluminas, the said substrate being uncoatedor coated with metallic substances, for instance aluminium, gold,silver, platinum, copper or bronze, or with metal oxides, for instancetitanium dioxide, iron oxide or chromium oxide, and mixtures thereof.

The nacreous pigments may be chosen from white nacreous pigments such asmica coated with titanium or with bismuth oxychloride, coloured nacreouspigments such as titanium mica coated with iron oxides, titanium micacoated especially with ferric blue or with chromium oxide, titanium micacoated with an organic pigment of the abovementioned type, and alsonacreous pigments based on bismuth oxychloride. Interference pigments,especially liquid-crystal or multilayer interference pigments, may alsobe used.

The term “alkyl” mentioned in the compounds cited above especiallydenotes an alkyl group containing from 1 to 30 carbon atoms andpreferably containing from 5 to 16 carbon atoms.

Hydrophobic-treated pigments are described especially in patentapplication EP-A-1 086 683.

The water-soluble dyes are, for example, beetroot juice or methyleneblue.

The synthetic or natural liposoluble dyes are, for example, DC Red 17,DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls(capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinolineyellow, annatto and curcumin.

The dyestuffs, in particular the pigments treated with a hydrophobicagent, may be present in the composition in a content ranging from 0.1%to 50% by weight, preferably ranging from 0.5% to 30% by weight andpreferentially ranging from 1% to 20% by weight, relative to the totalweight of the composition.

Fillers:

The composition according to the invention may comprise at least onefiller.

For the purposes of the present invention, the term “filler” denotessolid particles of any form, which are in an insoluble form anddispersed in the medium of the composition, even at temperatures thatmay be up to the melting point of all the fatty substances of thecomposition.

Generally, the fillers used according to the invention are colourless orwhite, namely non-pigmentary, i.e. they are not used to give aparticular colour or shade to the composition according to theinvention, even though their use may inherently lead to such a result.These fillers serve especially to modify the rheology or texture of thecomposition.

In this respect, they are different from nacres, organic pigmentarymaterials, for instance carbon black, pigments of D&C type, and lakesbased on cochineal carmine or on barium, strontium, calcium oraluminium, and inorganic pigmentary materials, for instance titaniumdioxide, zirconium oxide or cerium oxide, and also iron oxides (black,yellow or red), chromium oxide, manganese violet, ultramarine blue,chromium hydrate and ferric blue, which are, themselves, used to give ashade and coloration to the compositions incorporating them.

For the purposes of the invention, such compounds are not covered by thedefinition of fillers, which thus covers non-pigmentary fillers, whichmay be organic or inorganic.

The non-pigmentary fillers used in the compositions according to thepresent invention may be of lamellar, globular or spherical form, offibre type, or of any intermediate form between these defined forms.

The size of the particles, i.e. their granulometry, is chosen so as toensure the good dispersion of the fillers in the composition accordingto the invention. The granulometry of the particles may be distributedwithin the range from 5 μm to 10 nm and in particular from 10 μm to 10nm.

The fillers according to the invention may or may not be surface-coated,in particular surface-treated with silicones, amino acids, fluoroderivatives or any other substance that promotes the dispersion andcompatibility of the filler in the composition.

Mineral Fillers

For the purposes of the present invention, the terms “mineral” and“inorganic” are used interchangeably.

Among the non-pigmentary mineral fillers that may be used in thecompositions according to the invention, mention may be made of talc,mica, silica, perlite, which is especially commercially available fromthe company World Minerals Europe under the trade name Perlite P1430,Perlite P2550 or Perlite P204, kaolin, precipitated calcium carbonate,magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, boronnitride, hollow silica microspheres (Silica Beads® from Maprecos), andglass or ceramic microcapsules, and mixtures thereof.

According to one embodiment, the cosmetic composition according to theinvention comprises at least one non-pigmentary mineral filler chosenfrom the group comprising kaolin, talc, silica, perlite and clay, andmixtures thereof.

Organic Fillers

Among the organic fillers that may be mentioned are polyamide powder(Orgasol® Nylon® from Atochem), poly-β-alanine powder and polyethylenepowder, lauroyllysine, starch, tetrafluoroethylene polymer powders(Teflon®), hollow polymer microspheres such as those of polyvinylidenechloride/acrylonitrile, for instance Expancel® (Nobel Industrie) or ofacrylic acid copolymer (such as Polytrap (Dow Corning)), acrylatecopolymers, PMMA, 12-hydroxystearic acid oligomer stearate and siliconeresin microbeads (for example Tospearls® from Toshiba), magnesiumcarbonate, magnesium hydrogen carbonate, and metal soaps derived fromorganic carboxylic acids containing from 8 to 22 carbon atoms andpreferably from 12 to 18 carbon atoms, for example zinc stearate,magnesium stearate, lithium stearate, zinc laurate or magnesiummyristate, and mixtures thereof.

For the purposes of the present invention, the organic fillers aredifferent from the pigments.

They may also be particles comprising a copolymer, the said copolymercomprising trimethylol hexyl lactone. In particular, it may be ahexamethylene diisocyanate/trimethylol hexyl lactone copolymer. Suchparticles are especially commercially available, for example under thename Plastic Powder D-400® or Plastic Powder D-800® from the companyToshiki.

According to one embodiment, a composition of the invention may compriseat least one filler chosen from talc, silica, starch, clay, kaolin andperlite, and mixtures thereof.

One or more dispersants may be used, where appropriate, to protect thedispersed fillers or particles against aggregation or flocculation. Theymay be added independently of the solid fillers or particles or in theform of a colloidal dispersion of particles.

The concentration of dispersants is chosen so as to obtain satisfactorydispersion of the solid particles (without flocculation).

This dispersant may be a surfactant, an oligomer, a polymer or a mixtureof several thereof, bearing one or more functionalities with strongaffinity for the surface of the particles to be dispersed. Inparticular, poly(12-hydroxystearic acid) esters are used, such aspoly(12-hydroxystearic acid) stearate with a molecular weight of about750 g/mol, such as the product sold under the name Solsperse 21 000® bythe company Avecia, esters of poly(12-hydroxystearic acid) with polyolssuch as glycerol or diglycerol, such as polyglyceryl-2dipolyhydroxystearate (CTFA name) sold under the reference DehymulsPGPH® by the company Henkel (or diglyceryl poly(12-hydroxystearate)), oralternatively poly(12-hydroxystearic acid), such as the product soldunder the reference Arlacel P100 by the company Uniqema, and mixturesthereof.

As other dispersants that may be used in the composition of theinvention, mention may be made of quaternary ammonium derivatives ofpolycondensate fatty acids, for instance Solsperse 17 000® sold by thecompany Avecia, and mixtures of polydimethylsiloxane/oxypropylene suchas those sold by the company Dow Corning under the references DC2-5185and DC2-5225 C.

A composition of the invention should be cosmetically ordermatologically acceptable, i.e. it should contain a non-toxicphysiologically acceptable medium that can be applied to human lips. Forthe purposes of the invention, the term “cosmetically acceptable” refersto a composition of pleasant appearance, odour and feel.

The composition according to the invention may also contain ingredientscommonly used in cosmetics, such as vitamins, thickeners, traceelements, softeners, sequestrants, fragrances, acidifying agents,basifying agents, preserving agents, sunscreens, surfactants,antioxidants, hair-loss counteractants, antidandruff agents andpropellants, or mixtures thereof.

Needless to say, a person skilled in the art will take care to selectthis or these optional additional compounds, and/or the amount thereof,such that the advantageous properties of the corresponding compositionaccording to the invention are not, or are not substantially, adverselyimpaired by the envisaged addition.

According to another aspect, the invention also relates to a cosmeticassembly comprising:

i) a container delimiting at least one compartment, the said containerbeing closed by a closing member; and

ii) a composition placed inside the said compartment, the compositionbeing in accordance with the invention.

The container may be in any adequate form. It may especially be in theform of a bottle, a tube, a jar, a case, a box, a sachet or a carton.

The closing member may be in the form of a removable stopper, a lid, acap, a tear-off strip or a capsule, especially of the type comprising abody attached to the container and a cover cap articulated on the body.It may also be in the form of a member for selectively closing thecontainer, especially a pump, a valve or a flap valve.

The container may be combined with an applicator, especially in the formof a brush comprising an arrangement of bristles maintained by a twistedwire. Such a twisted brush is described especially in U.S. Pat. No.4,887,622. It may also be in the form of a comb comprising a pluralityof application members, obtained especially by moulding. Such combs aredescribed, for example, in patent FR 2 796 529. The applicator may be inthe form of a fine brush, as described, for example, in patent FR 2 722380. The applicator may be in the form of a block of foam or ofelastomer, a felt or a spatula. The applicator may be free (tuft orsponge) or securely fastened to a rod borne by the closing member, asdescribed, for example, in U.S. Pat. No. 5,492,426. The applicator maybe securely fastened to the container, as described, for example, inpatent FR 2 761 959.

The product may be contained directly in the container, or indirectly.By way of example, the product may be arranged on an impregnatedsupport, especially in the form of a wipe or a pad, and arranged(individually or in plurality) in a box or in a sachet. Such a supportincorporating the product is described, for example, in patentapplication WO 01/03538.

The closing member may be coupled to the container by screwing.Alternatively, the coupling between the closing member and the containeris done other than by screwing, especially via a bayonet mechanism, byclick-fastening, gripping, welding, bonding or by magnetic attraction.The term “click-fastening” in particular means any system involving thecrossing of a bead or cord of material by elastic deformation of aportion, especially of the closing member, followed by return to theelastically unconstrained position of the said portion after thecrossing of the bead or cord.

The container may be at least partially made of thermoplastic material.Examples of thermoplastic materials that may be mentioned includepolypropylene or polyethylene.

Alternatively, the container is made of non-thermoplastic material,especially glass or metal (or alloy).

The container may have rigid walls or deformable walls, especially inthe form of a tube or a tubular bottle.

The container may comprise means for distributing or facilitating thedistribution of the composition. By way of example, the container mayhave deformable walls so as to allow the composition to exit in responseto a positive pressure inside the container, this positive pressurebeing caused by elastic (or non-elastic) squeezing of the walls of thecontainer. Alternatively, especially when the product is in the form ofa stick, the product may be driven out by a piston mechanism. Still inthe case of a stick, especially of makeup product (lipstick, foundation,etc.), the container may comprise a mechanism, especially a rackmechanism, a threaded-rod mechanism or a helical groove mechanism, andmay be capable of moving a stick in the direction of the said aperture.Such a mechanism is described, for example, in patent FR 2 806 273 or inpatent FR 2 775 566. Such a mechanism for a liquid product is describedin patent FR 2 727 609.

The container may be formed from a carton with a base delimiting atleast one housing containing the composition, and a lid, especiallyarticulated on the base, and capable of at least partially covering thesaid base. Such a carton is described, for example, in patentapplication WO 03/018423 or in patent FR 2 791 042.

The container may be equipped with a drainer arranged in the region ofthe aperture of the container. Such a drainer makes it possible to wipethe applicator and possibly the rod to which it may be securelyfastened. Such a drainer is described, for example, in patent FR 2 792618.

The composition may be at atmospheric pressure inside the container (atroom temperature) or pressurized, especially by means of a propellentgas (aerosol). In the latter case, the container is equipped with avalve (of the type used for aerosols).

Protocol for Measuring the Transfer:

The transfer index of the deposit obtained with the compositionaccording to the invention is determined according to the measuringprotocol described below.

A support (40 mm×70 mm rectangle) consisting of an acrylic coating(hypoallergenic acrylic adhesive on polyethylene film sold under thename Blenderme ref. FH5000-55113 by the company 3M Santé) bonded onto alayer of polyethylene foam that is adhesive on the side opposite the oneto which the adhesive plaster is fixed (foam layer sold under the nameRE 40×70EP3 from the company Joint Technique Lyonnais Ind.) is prepared.

The colour L*₀a*₀b*₀ of the support, on the acrylic coating side, ismeasured using a Minolta CR300 colorimeter.

The support thus prepared is preheated on a hotplate maintained at atemperature of 40° C. so that the surface of the support is maintainedat a temperature of 33° C.±1° C.

While leaving the support on the hotplate, the composition is applied tothe entire non-adhesive surface of the support (i.e. to the surface ofthe acrylic coating), spreading it out with a brush to obtain a depositof the composition of about 15 μm, and this deposit is then left to dryfor 10 minutes.

After drying, the colour L*a*b* of the film thus obtained is measured.

The colour difference ΔE1 between the colour of the film relative to thecolour of the naked support is then determined via the followingrelationship:

ΔE1=√{square root over ((L*−L ₀*)²+(a*−a ₀*)²+(b*−b ₀*)²)}{square rootover ((L*−L ₀*)²+(a*−a ₀*)²+(b*−b ₀*)²)}{square root over ((L*−L₀*)²+(a*−a ₀*)²+(b*−b ₀*)²)}

The support is then bonded via its adhesive face (adhesive face of thefoam layer) to an anvil 20 mm in diameter and equipped with a screwpitch. A sample of the support/deposit assembly is then cut out using asample punch 18 mm in diameter. The anvil is then screwed onto a press(Statif Manuel Imada SV-2 from the company Someco) equipped with atensile testing machine (Imada DPS-20 from the company Someco).

A strip 33 mm wide and 29.7 cm long is drawn on a sheet of whitephotocopier paper with a basis weight of 80 g/m², a first line is marked2 cm from the edge of the sheet, and a second line is then marked 5 cmfrom the edge of the sheet, the first and second lines thus delimiting abox on the strip; next, a first mark and a second mark located in thestrip at reference points 8 cm and 16 cm, respectively, from the secondmark, are applied. 20 μl of water are placed on the first mark and 10 μlof refined sunflower oil (sold by the company Lesieur) are placed on thesecond mark.

The white paper is placed on the base of the press and the sample placedon the box of the strip of paper is then pressed at a pressure of about300 g/cm² exerted for 30 seconds. The press is then opened and thesample is again placed just after the second mark (i.e. next to thebox), a pressure of about 300 g/cm² is again exerted, and the paper isdisplaced, in a rectilinear manner as soon as the contact is made, at aspeed of 1 cm/s over the entire length of the strip such that the samplepasses through the water and oil deposits.

After removing the sample, some of the deposit has transferred onto thepaper. The colour L*', a*', b*' of the deposit remaining on the sampleis then measured.

The colour difference ΔE2 between the colour of the deposit remaining onthe sample relative to the colour of the naked support is thendetermined via the following relationship:

ΔE2=√{square root over ((L*′−L ₀*)²+(a*′−a ₀*)²+(b*′−b ₀*)²)}{squareroot over ((L*′−L ₀*)²+(a*′−a ₀*)²+(b*′−b ₀*)²)}{square root over((L*′−L ₀*)²+(a*′−a ₀*)²+(b*′−b ₀*)²)}

The transfer index of the composition, expressed as a percentage, isequal to the ratio:

100×ΔE2/ΔE1

The measurement is performed on 6 supports in succession and thetransfer index corresponds to the mean of the six measurements obtainedwith the six supports.

The present invention also relates to a cosmetic product for making upand/or caring for keratin materials, comprising at least twocompositions that can be applied successively to keratin materials,especially to the lips.

The present invention also relates to a process for making up the faceand the body using these two compositions. They are preferably appliedsuccessively to the keratin materials: the first composition and thenthe second composition.

These two compositions are conventionally known as a topcoat and abasecoat.

Thus, according to this embodiment, the invention relates to a product(also known as a kit) for making up and/or caring for keratin materials,especially the lips, comprising a first composition and a secondcomposition conditioned in separate containers,

the first composition containing, in a physiologically acceptablemedium:

a) a siloxane resin comprising the following units:

(i) (R¹ ₃SiO_(1/2))_(a)

(ii) (R² ₂SiO_(2/2))_(b)

(iii) (R³SiO_(3/2))_(c) and

(iv) (SiO_(4/2))_(d)

with

R¹, R² and R³ independently representing an alkyl group containing from1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,

a being between 0.05 and 0.5,

b being between 0 and 0.3,

c being greater than 0,

d being between 0.05 and 0.6,

a+b+c+d=1,

on condition that more than 40 mol % of the groups R³ of the siloxaneresin are propyl groups, and

b) at least one liquid fatty phase, and

c) at least one film-forming polymer chosen from the group comprising:

-   -   a film-forming block ethylenic polymer, comprising at least a        first block and at least a second block, is characterized in        that the first block is obtained from at least one acrylate        monomer of formula CH₂═CH—COOR₂ in which R₂ represents a C₄ to        C₁₂ cycloalkyl group and at least one methacrylate monomer of        formula CH₂═C(CH₃)—COOR₂ in which R′₂ represents a C₄ to C₁₂        cycloalkyl group, and characterized in that the second block is        obtained from an acrylic acid monomer and from at least one        monomer with a glass transition temperature of less than or        equal to 20° C.,    -   a vinyl polymer comprising at least one carbosiloxane        dendrimer-based unit,    -   a dispersion of acrylic or vinyl radical homopolymer or        copolymer particles dispersed in the said liquid fatty phase,

and the second composition, which is different from the first,comprising at least one fatty substance.

The fatty substance of the second composition is preferably chosen fromwaxes and non-volatile oils.

According to one preferred embodiment, the second composition comprisesat least one wax and at least one non-volatile oil.

Advantageously, the wax is a sunflower wax.

Preferably, the non-volatile oil is an oil such as caprylic/capric acidtriglycerides.

The presence of a second composition applied over the first compositiononto the keratin materials can especially improve the gloss and/orcomfort properties.

The content of all the patents or patent applications cited previouslyis incorporated by reference into the present patent application.

In the patent application, unless specifically mentioned otherwise, thecontents are expressed on a weight basis relative to the total weight ofthe composition.

The invention is illustrated in greater detail by the examples describedbelow, which are given as non-limiting illustrations. The percentagesare weight percentages.

EXAMPLE 1 Preparation of the Siloxane Resins

The following resins are used:

MQ resin=an MQ resin of formula M_(0.43)Q_(0.57) and of M_(n)=3230dissolved in xylene to a proportion of 70.8% by weight of solids. The MQresin was manufactured according to the techniques described by Daudt inU.S. Pat. No. 2,676,182.

T Propyl resin=a propyl silsesquioxane resin at 74.8% by weight intoluene. The propyl silsesquioxane resin was obtained by hydrolysis ofpropyltrichlorosilane.

Preparation of the MQT^(Pr) Resins

An MQ resin, a T propyl resin, xylene and 1M KOH in water in theproportions presented in Table 1 are introduced into a 3-necked flaskequipped with a stirrer, a temperature probe and Dean-Stark apparatusmounted with a condenser. Xylene is pre-introduced into the Dean-Starkapparatus so as to ensure maintenance of a level of solids of 50% in thereactor. The mixture in the reactor is refluxed (between 100 and 140°C.) for at least 3 hours. Any water formed in the reaction mixture iscontinuously removed and trapped in the form of an azeotrope in theDean-Stark apparatus. After refluxing for 3 hours, the water is removedfrom the apparatus and heating is continued for a further 30 minutes.After cooling the mixture, an excess of acetic acid is added toneutralize the KOH in the mixture. The mixture is then filtered toremove the salts formed, by passing it through a filter under pressure.Solvent exchange is performed by heating the mixture in a rotaryevaporator under vacuum. After removing the majority of the xylene,decamethylcyclopentasiloxane (or isododecane) is added while continuingto remove any residual aromatic solvent. The structures of the resultingsiloxane resins are characterized by ²⁹Si NMR and GPC, and the resultsare summarized in Table 2 below.

TABLE 1 Weight Weight Weight Weight Mass ratio % of % of T Weight % of %of of MQ/T^(Pr) MQ propyl % of 1M acetic Example # resins added resinresin xylene KOH acid 1-a (85:15) 59.4 10.5 29.1 0.9 0.2 1-b (50:50)34.9 34.8 29.1 0.9 0.2 1-c (30:70) 20.9 48.8 29.2 0.9 0.2 1-d (95:5) 67.1 3.5 28.3 0.9 0.2 1-e (100:0)  69.3 0 28.8 0.9 0.2

TABLE 2 Resin structure Weight according to NMR % of Example #characterization OH Mn Mw Mw/Mn MQ resin M^(0.43)Q^(0.57) 3230    15164.7 T Propyl T^(Pr) _(1.0) 7.0 3470    11 400 3.3 resin 1-aM_(0.374)Q_(0.529):T^(Pr) _(0.097) 1.4 5880   271 000 46.1 1-bM_(0.248)Q_(0.341):T^(Pr) _(0.412) 2.1 6640  3 860 000 581.3 1-cM_(0.162)Q_(0.217):T^(Pr) _(0.621) 1.5 7600 25 300 000 3329 1-dM_(0.419)Q_(0.5485):T^(Pr) _(0.03) 1.5 1-e MQ 1.7 5200    28 900 5.6

EXAMPLE 2 Preparation of a Poly(Isobornyl Acrylate/IsobornylMethacrylate/Isobutyl Acrylate/Acrylic Acid) Polymer

300 g of isododecane are introduced into a 1-litre reactor and thetemperature is then raised so as to pass from room temperature (25° C.)to 90° C. over 1 hour.

105 g of isobornyl methacrylate (manufactured by Arkema), 105 g ofisobornyl acrylate (manufactured by Arkema) and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 fromAkzo Nobel) are then added, at 90° C. and over 1 hour.

The mixture is maintained at 90° C. for 1 hour 30 minutes.

75 g of isobutyl acrylate (manufactured by Fluka), g of acrylic acid and1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are thenintroduced into the preceding mixture, still at 90° C. and over 30minutes.

The mixture is maintained at 90° C. for 3 hours, and is then cooled.

A solution containing 50% polymer active material in isododecane isobtained.

A polymer comprising a first poly(isobornyl acrylate/isobornylmethacrylate) rigid block with a Tg of 110° C., a second poly(isobutylacrylate/acrylic acid) flexible block with a Tg of −9° C. and anintermediate block, which is an isobornyl acrylate/isobornylmethacrylate/isobutyl acrylate/acrylic acid random polymer, is obtained.

EXAMPLES 3 AND 4 Liquid Lipsticks

Compositions 3 and 4 below were prepared:

Composition Composition 4 3 comparative Weight Weight percentagespercentages Compounds % % 2-Octyldodecanol 9.43 8.23 Refined plantperhydrosqualene 5.05 4.21 (Phytosqualan from Sophim) Brilliant yellowFCF aluminium lake on 2.58 2.58 alumina (42/58) (CI: 15985:1 + 77002)Brilliant blue FCF aluminium lake on 0.16 0.16 alumina (12/88) (CI:42090:2 + 77002) Calcium salt of Lithol B Red 0.59 0.59 Rutile titaniumoxide treated with 2.74 2.74 alumina/silica/trimethylolpropane (CI:77891) Black iron oxide (CI: 77499) 0.32 0.32 Mixture of isopropyl,isobutyl and n- 0.65 0.65 butyl p-hydroxybenzoates (40/30/30) (LiquaparOil from ISP) Polyphenyltrimethylsiloxydiphenylsiloxane 25.03 25.03(viscosity: 1000 cSt-MW: 3000 - g/mol) (Belsil PDM 1000 from Wacker)Mica-titanium dioxide-brown iron oxide 2 2 (77/21/4) (size: 16-128microns) Fragrance 0.3 0.3 Polybutylene (monoolefins/isoparaffins) 10.6510.65 (MW: 920) (Indopol H 100 from Ineos) Poly(isobornylmethacrylate-co-isobornyl 30 37.04 acrylate-co-isobutylacrylate-co-acrylic acid) as prepared in Example 2 above (50% of polymerin 50% of isododecane) MQ-T propyl resin (30:70) in isododecane 5.1 — asprepared in Example 1 above, from Dow Corning Hydrophilic fumed silica(Aerosil 200 0.5 0.5 from Evonik Degussa) Hydrophobic fumed silica,surface-treated 5 5 with dimethylsilane (Aerosil 972 from EvonikDegussa) Total: 100 100

Procedure:

-   -   a. The fillers and pigments optionally present are ground in        part of the oily phase.    -   b. The rest of the liposoluble ingredients are then mixed        together at a temperature of about 100° C. The ground mixture is        then added to the oily phase.    -   c. The mixture is stirred with a Rayneri blender for 45 minutes,        and the siloxane resin is added at room temperature.    -   d. The formulation is poured into isododecane-leaktight heating        bags.

Composition 3 according to the invention contains 15% polymer (weight ofsolids) prepared according to Example 2 and 3.5% (weight of solids) ofsiloxane resin prepared according to Example 1-C), i.e. in total 18.5%of film-forming polymer.

Comparative composition 4 contains 18.5% of polymer (weight of solids)prepared according to Example 2.

Comparative composition 4 is very viscous and tacky and is very thick onapplication. It is uncomfortable on the lips since the film formed isvery thick and tacky.

Composition 3 according to the invention is much more pleasant(slippery) on application and it forms a much finer and more comfortabledeposit.

EXAMPLES 5 AND 6 Liquid Lipsticks

The following lipstick formulation was prepared (same procedure as thatdescribed previously).

Composition 5 according to the Comparative invention (Weight composition6 Compounds percentages %) (Weight percentages %) Butyl acrylatecopolymer containing 31.25 37.5 dendritic silicone side chains:[tris(trimethylsiloxy)siloxyethyldimethyl- siloxy]silylpropylmethacrylate in isododecane: 40/60 (Dow Corning FA 4002 ID SiliconeAcrylate from Dow Corning) MQ-T propyl resin (30/70) in isododecane as 4— prepared in Example 1-C above, from Dow Corning Isododecane from Ineos1.3 — Refined plant perhydrosqualene 12.02 12.02 (Phytosqualan fromSophim) Octyldodecanol 14.2 13.62 Polybutene (Indopol H 100 from Ineos)10.65 10.65 Isopropyl paraben (and) isobutyl paraben 0.65 0.65 (and)butyl paraben (Liquapar Oil from ISP) Red 7 (Unipure Red LC 3079 OR fromLCW 0.23 0.23 (Sensient)) Iron oxides (Sunpuro Black Iron Oxide C33-0.05 0.05 7001 from Sun) Mica (and) titanium dioxide (and) iron 1 1oxides (Cloisonne Sparkle Gold 222 J from Engelhard) Calcium aluminiumborosilicate (and) silver 2.5 2.5 (Metashine ME 2040 PS from NError!Hyperlink reference not valid.) Trimethylsiloxyphenyl Dimethicone(Belsil 16.65 16.3 PDM 1000 from Wacker) Silica Dimethyl SilylateAerosil R 972 from 5 5 EError! Hyperlink reference not valid. Silica(Aerosil 200 from EError! Hyperlink 0.5 0.5 reference not valid.) Total100 100

The staying power of compositions 5 and 6 is evaluated according to thetransfer index measurement protocol described above. The resultsobtained are as follows:

The two compositions 5 and 6 have substantially the same solids contentof film-forming polymer (siloxane resin vinyl polymer containingcarbosiloxane dendrimer-based units).

For composition 5 according to the invention containing a vinyl polymercomprising at least one carbosiloxane dendrimer-based unit and an MQ-Tpropyl siloxane resin, a transfer index value of 31.81±7.87 is measured.

For comparative composition 6 containing no siloxane resin, a transferindex value of 18.32±0.56 is measured.

1. A process for making up and/or caring for keratin materials,comprising: applying to the keratin materials a composition, comprisingin a physiologically acceptable medium: a) a siloxane resin comprisingthe following units: (i) (R¹ ₃SiO_(1/2))_(a) (ii) (R² ₂SiO_(2/2))_(b)(iii) (R³SiO_(3/2))_(c) and (iv) (SiO_(4/2))_(d) wherein R¹, R² and R³are each independently an alkyl group containing from 1 to 8 carbonatoms, an aryl group, a carbinol group or an amino group, a is between0.05 and 0.5, b is between 0 and 0.3, c is greater than 0, d is between0.05 and 0.6, a+b+c+d=1, with the proviso that more than 40 mol % of thegroups R³ of the siloxane resin are propyl groups, and b) at least oneliquid fatty phase, and c) at least one film-forming polymer chosen fromthe group comprising: a film-forming block ethylenic polymer, comprisingat least a first block and at least a second block, wherein the firstblock is obtained from at least one acrylate monomer of formulaCH₂═CH—COOR₂ R₂ represents a C₄ to C₁₂ cycloalkyl group and at least onemethacrylate monomer of formula CH₂═C(CH₃)—COOR′₂ wherein R′₂ representsa C₄ to C₁₂ cycloalkyl group, and the second block is obtained from anacrylic acid monomer and from at least one monomer with a glasstransition temperature of less than or equal to 20° C., a vinyl polymercomprising at least one carbosiloxane dendrimer-based unit, a dispersionof acrylic or vinyl radical homopolymer or copolymer particles dispersedin the said liquid fatty phase.
 2. The process for making up and/orcaring for keratin materials according to claim 1, wherein the saidsiloxane resin comprises: (i) (R¹ ₃SiO_(1/2))_(a) (iii)(R³SiO_(3/2))_(c) and (iv) (SiO_(4/2))_(d) wherein R¹ and R³ eachindependently is an alkyl group containing from 1 to 8 carbon atoms, ais between 0.05 and 0.5 , c is greater than zero, d is between 0.05 and0.6, a+b+c+d=1, with the proviso that more than 40 mol % of the groupsR³ of the siloxane resin are propyl groups.
 3. The process for making upand/or caring for keratin materials according to claim 1 wherein thesaid siloxane resin is obtained via a process comprising reactionbetween: A) an MQ resin comprising at least 80 mol % of units (R¹₃SiO_(1/2))_(a) and (SiO_(4/2))_(d) wherein R¹ is a methyl group, a andd are greater than zero, a ratio a/d is between 0.5 and 1.5; and B) a Tpropyl resin comprising at least 80 mol % of units (R³SiO_(3/2))_(c),wherein R³ is a propyl group, c is greater than zero, in which a massratio A/B is between 95/5 and 15/85 .
 4. The process for making upand/or caring for keratin materials according to claim 1, wherein thefilm-forming block ethylenic polymer comprises an intermediate blockcomprising at least one constituent monomer of the first block and atleast one constituent monomer of the second block, and a polydispersityindex of the film-forming block ethylenic polymer is greater than
 2. 5.The process for making up and/or caring for keratin materials accordingto claim 1, wherein, the second block of the film-forming blockethylenic polymer is obtained from polymerization of acrylic acid andisobutyl acrylate, and the first block is obtained from polymerizationof isobornyl acrylate and isobornyl methacrylate.
 6. The process formaking up and/or caring for keratin materials according to claim 1,wherein the vinyl polymer comprises at least one carbosiloxane dendrimerof formula (I):

wherein Z is a divalent organic group, p is 0 or 1, R¹ is an aryl oralkyl group of 1 to 10 carbon atoms and X^(i) is a silylalkyl group offormula (II):

wherein R¹ is an aryl or alkyl group of 1 to 10 carbon atoms, R² is analkylene group of 1 to 10 carbon atoms, R³ is an alkyl group of 1 to 10carbon atoms, and X^(i+1) is a group selected from the group consistingof hydrogen atoms, aryl groups and alkyl groups containing up to 10carbon atoms, and silylalkyl groups the index i is an integer from 1 to10 indicating the generation of the silylalkyl group starting in eachcarbosiloxane dendritic structure with a value of 1 for the group X^(i)in formula (I) and the index a^(i) is an integer from 0 to
 3. 7. Theprocess for making up and/or caring for keratin materials according toclaim 1, wherein the dispersion of homopolymer or copolymer particlescomprises polymer particles in dispersion selected from acrylic polymersor copolymers which are insoluble in water-soluble alcohols.
 8. Theprocess for making up and/or caring for keratin materials according toclaim 1, wherein a content of the film-forming polymer is from 0.1% to60% by weight of film-forming polymer solids.
 9. The process for makingup and/or caring for keratin materials according to claim 1, wherein atotal solids content of the siloxane resin is from 1% to 80% by weightrelative to the total weight of the composition.
 10. The process formaking up and/or caring for keratin materials claim 1, wherein thecomposition comprises less than 3% by weight of water relative to thetotal weight of the composition.
 11. The process for making up and/orcaring for keratin materials according to claim 1, wherein thecomposition further comprises at least one structuring agent selectedfrom the group consisting of thickeners, organogelling agents, waxes,pasty fatty substances and gums.
 12. The process for making up and/orcaring for keratin materials according to claim 1, wherein thecomposition further comprises at least one other oil, which isnon-volatile.
 13. The process for making up and/or caring for keratinmaterials according to claim 1, wherein the composition furthercomprises at least one dyestuff and/or at least one filler.
 14. Acomposition for making up and/or caring for keratin materials,comprising, in a physiologically acceptable medium: a) a siloxane resincomprising the following units: (i) (R¹ ₃SiO_(1/2))_(a) (ii) (R²₂SiO_(2/2))_(b) (iii) (R³SiO_(3/2))_(c) and (iv) (SiO_(4/2))_(d) (i) (R¹₃SiO_(1/2))_(a) (ii) (R² ₂SiO_(2/2))_(b) (iii) (R³SiO_(3/2))_(c) and(iv) (SiO_(4/2))_(d) wherein R¹, R² and R³ are each independently analkyl group containing from 1 to 8 carbon atoms, an aryl group, acarbinol group or an amino group, a is between 0.05 and 0.5, b isbetween 0 and 0.3, c is greater than 0, d is between 0.05 and 0.6,a+b+c+d=1, with the proviso that more than 40 mol % of the groups R³ ofthe siloxane resin are propyl groups, and b) at least one liquid fattyphase, and c) at least one film-forming polymer chosen from the groupcomprising: a film-forming block ethylenic polymer, comprising at leasta first block and at least a second block, wherein the first block isobtained from at least one acrylate monomer of formula CH₂═CH—COOR₂ R₂represents a C₄ to C₁₂ cycloalkyl group and at least one methacrylatemonomer of formula CH₂═C(CH₃)—COOR′₂ in which wherein R′₂ represents aC₄ to C₁₂ cycloalkyl group, and the second block is obtained from anacrylic acid monomer and from at least one monomer with a glasstransition temperature of less than or equal to 20° C., a vinyl polymercomprising at least one carbosiloxane dendrimer-based unit, a dispersionof acrylic or vinyl radical homopolymer or copolymer particles dispersedin the said liquid fatty phase.
 15. A product for making up and/orcaring for keratin materials, comprising a first composition and asecond composition conditioned in separate containers, wherein the firstcomposition comprises, in a physiologically acceptable medium: a) asiloxane resin comprising the following units: (i) (R¹ ₃SiO_(1/2))_(a)(ii) (R² ₂SiO_(2/2))_(b) (iii) (R³SiO_(3/2))_(c) and (iv)(SiO_(4/2))_(d) wherein R¹, R² and R³ are each independently an alkylgroup containing from 1 to 8 carbon atoms, an aryl group, a carbinolgroup or an amino group, a is between 0.05 and 0.5, b is between 0 and0.3, c is greater than 0, d is between 0.05 and 0.6, a+b+c+d=1, with theproviso that more than 40 mol % of the groups R³ of the siloxane resinare propyl groups, and b) at least one liquid fatty phase, and c) atleast one film-forming polymer selected from the group consisting of: afilm-forming block ethylenic polymer, comprising at least a first blockand at least a second block, wherein the first block is obtained from atleast one acrylate monomer of formula CH₂═CH—COOR₂ R₂ represents a C₄ toC₁₂ cycloalkyl group and at least one methacrylate monomer of formulaCH₂═C(CH₃)—COOR′₂ wherein R′₂ represents a C₄ to C₁₂ cycloalkyl group,and the second block is obtained from an acrylic acid monomer and fromat least one monomer with a glass transition temperature of less than orequal to 20° C.; a vinyl polymer comprising at least one carbosiloxanedendrimer-based unit; and a dispersion of acrylic or vinyl radicalhomopolymer or copolymer particles dispersed in the said liquid fattyphase; and the second composition, which is different from the first,comprises at least one fatty substance.